Home Cart 0 Sign in  
X

[ CAS No. 4466-24-4 ] {[proInfo.proName]}

,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
HazMat Fee +

There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.

Type HazMat fee for 500 gram (Estimated)
Excepted Quantity USD 0.00
Limited Quantity USD 15-60
Inaccessible (Haz class 6.1), Domestic USD 80+
Inaccessible (Haz class 6.1), International USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic USD 100+
Accessible (Haz class 3, 4, 5 or 8), International USD 200+
3d Animation Molecule Structure of 4466-24-4
Chemical Structure| 4466-24-4
Chemical Structure| 4466-24-4
Structure of 4466-24-4 * Storage: {[proInfo.prStorage]}
Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Quality Control of [ 4466-24-4 ]

Related Doc. of [ 4466-24-4 ]

Alternatived Products of [ 4466-24-4 ]

Product Details of [ 4466-24-4 ]

CAS No. :4466-24-4 MDL No. :MFCD00047071
Formula : C8H12O Boiling Point : -
Linear Structure Formula :- InChI Key :NWZIYQNUCXUJJJ-UHFFFAOYSA-N
M.W : 124.18 Pubchem ID :20534
Synonyms :

Safety of [ 4466-24-4 ]

Signal Word:Danger Class:3
Precautionary Statements:P210-P233-P240-P241+P242+P243-P280-P303+P361+P353-P370+P378-P403+P235-P501 UN#:3271
Hazard Statements:H225 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 4466-24-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 4466-24-4 ]

[ 4466-24-4 ] Synthesis Path-Downstream   1~87

  • 1
  • [ 4208-63-3 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide; hydrazine hydrate; diethylene glycol
  • 2
  • [ 110-00-9 ]
  • [ 109-65-9 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
85% With n-butyllithium In tetrahydrofuran 0 deg C, room temperature, 4 h;
With n-butyllithium 1) THF, hexane, 24h, RT, 2) 24h, RT; Yield given. Multistep reaction;
With n-butyllithium 1.) -30 deg C, 4 h., n-hexane, dry THF; 2.) r.temp.; Yield given. Multistep reaction;
  • 3
  • [ 110-00-9 ]
  • [ 542-69-8 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: furan With n-butyllithium In tetrahydrofuran; hexane at -78 - -20℃; Stage #2: 1-iodo-butane In tetrahydrofuran; hexane at -20 - 20℃;
With n-butyllithium 1.) THF, hexane, -20 deg C, 2 h, 2.) -20 deg C, 1 h, 3.) 22 deg C, 1 h; Yield given. Multistep reaction;
  • 4
  • [ 4466-24-4 ]
  • [ 109-65-9 ]
  • [ 72636-53-4 ]
YieldReaction ConditionsOperation in experiment
70% With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; for 0.5h;
With n-butyllithium 1) THF, hexane, 24h, RT, 2) 24h; Yield given. Multistep reaction;
With n-butyllithium 1.) -30 deg C, 4 h., n-hexane, dry THF; 2.) r.temp.; Yield given. Multistep reaction;
  • 5
  • [ 4466-24-4 ]
  • [ 56-23-5 ]
  • [ 86269-36-5 ]
YieldReaction ConditionsOperation in experiment
86% In benzene at 50℃; for 2h;
  • 6
  • [ 4466-24-4 ]
  • [ 623-73-4 ]
  • (2E,4E)-6-Oxo-deca-2,4-dienoic acid ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: 2-Butylfuran; diazoacetic acid ethyl ester In dichloromethane at 20℃; for 10h; Stage #2: With iodine In dichloromethane at 20℃; for 12h;
  • 7
  • [ 6165-76-0 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
59% With carbon monoxide; triphenylphosphine; bis(dibenzylideneacetone)-palladium(0) In dichloromethane at 0℃; for 30h;
  • 8
  • [ 106-96-7 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
47% With carbon monoxide; bis(dibenzylideneacetone)-palladium(0); tris(para-trifluoromethyl)phenyl phosphine In methanol; dichloromethane at 0℃; for 40h;
  • 9
  • [ 4466-24-4 ]
  • (E)-dodec-7-en-5-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% Stage #1: 2-Butylfuran With tert.-butyl lithium In tetrahydrofuran; pentane at 0 - 3℃; for 0.5h; Stage #2: (n-C4H9)2CuLi In tetrahydrofuran; various solvents; pentane at -78 - 20℃;
  • 10
  • [ 4466-24-4 ]
  • [ 558472-48-3 ]
YieldReaction ConditionsOperation in experiment
78% Stage #1: 2-Butylfuran With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; Stage #2: With iodine In tetrahydrofuran; hexane at -78 - 0℃;
  • 11
  • [ 4466-24-4 ]
  • [ 3857-83-8 ]
  • [ 1005759-05-6 ]
YieldReaction ConditionsOperation in experiment
53% With potassium acetate; triphenylphosphine In N,N-dimethyl-formamide at 150℃; for 20h;
  • 12
  • [ 4466-24-4 ]
  • [ 17763-67-6 ]
  • [ 80866-26-8 ]
YieldReaction ConditionsOperation in experiment
51% With potassium acetate; triphenylphosphine In N,N-dimethyl-formamide at 150℃; for 20h;
  • 13
  • [ 4466-24-4 ]
  • [ 1089665-91-7 ]
  • [ 1089666-17-0 ]
  • [ 1089666-18-1 ]
YieldReaction ConditionsOperation in experiment
53% With n-butyllithium In hexane; toluene at -78℃; for 0.333333h; Inert atmosphere; optical yield given as %de; regioselective reaction;
  • 14
  • [ 4466-24-4 ]
  • [ 1089665-94-0 ]
  • [ 1089666-20-5 ]
  • [ 1089666-21-6 ]
YieldReaction ConditionsOperation in experiment
1: 37% 2: 6% With n-butyllithium In hexane; toluene at -78℃; for 0.75h; Inert atmosphere; optical yield given as %de; regioselective reaction;
  • 15
  • [ 4466-24-4 ]
  • [ 154345-11-6 ]
  • [ 1089666-02-3 ]
  • [ 1089666-03-4 ]
YieldReaction ConditionsOperation in experiment
52% With n-butyllithium In hexane; toluene at -78℃; for 0.25h; Inert atmosphere; optical yield given as %de; regioselective reaction;
  • 16
  • [ 4466-24-4 ]
  • [ 154345-10-5 ]
  • [ 1089666-77-2 ]
  • [ 1089666-04-5 ]
YieldReaction ConditionsOperation in experiment
54% With n-butyllithium In hexane; toluene at -78℃; for 0.5h; Inert atmosphere; optical yield given as %de; regioselective reaction;
  • 17
  • [ 4466-24-4 ]
  • [ 4701-17-1 ]
  • [ 32364-72-0 ]
  • [ 1062177-01-8 ]
  • 18
  • [ 4466-24-4 ]
  • [ 75-77-4 ]
  • [ 1160526-78-2 ]
YieldReaction ConditionsOperation in experiment
89% Stage #1: 2-Butylfuran With n-butyllithium In diethyl ether; hexane at -20 - 20℃; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 0 - 20℃;
  • 19
  • [ 4466-24-4 ]
  • [ 623-03-0 ]
  • [ 925459-26-3 ]
YieldReaction ConditionsOperation in experiment
90% With 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenylmethyl)ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
83% With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
68% With tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 40h; Inert atmosphere; Schlenk technique;
68 %Spectr. With tetrabutylammomium bromide; palladium diacetate; potassium carbonate In N,N-dimethyl acetamide at 150℃; for 40h; Inert atmosphere;

  • 20
  • [ 4466-24-4 ]
  • [ 6285-05-8 ]
  • [ 1253967-16-6 ]
YieldReaction ConditionsOperation in experiment
94% With 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenylmethyl)ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
84% With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
  • 21
  • [ 4466-24-4 ]
  • [ 873-32-5 ]
  • [ 1042318-52-4 ]
YieldReaction ConditionsOperation in experiment
87% With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
69% With tetrabutylammomium bromide; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 100℃; for 20h; Inert atmosphere;
34% With 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
  • 22
  • [ 4466-24-4 ]
  • [ 34841-35-5 ]
  • [ 1253967-17-7 ]
  • 23
  • [ 4466-24-4 ]
  • [ 100-00-5 ]
  • [ 925459-27-4 ]
YieldReaction ConditionsOperation in experiment
90% With 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
78% With tetrabutylammomium bromide; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 100℃; for 20h; Inert atmosphere;
74% With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
71% With [1,3-bis(naphthalen-1-ylmethyl)benzimidazol-2-ylidene]dichlorido[(3-chloropyridine-N)]palladium(II); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;

  • 24
  • [ 4466-24-4 ]
  • [ 98-56-6 ]
  • [ 1042318-49-9 ]
YieldReaction ConditionsOperation in experiment
90% With 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenylmethyl)ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
74% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 20h; Inert atmosphere; Schlenk technique;
73% With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
62% With C36H50Cl2N3OPPd; potassium carbonate; trimethylpyruvic acid In N,N-dimethyl acetamide at 110℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;
19% With dichloridobis[1-(2-methoxyethyl)-3-(naphthalen-1-ylmethyl)benzimidazol-2-ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;

  • 25
  • [ 4466-24-4 ]
  • [ 1245635-15-7 ]
  • [ 1245635-43-1 ]
  • [ 1245634-80-3 ]
YieldReaction ConditionsOperation in experiment
With (CH3)2CHMgCl-LiCl In tetrahydrofuran; diethyl ether pear-shaped flask charged (borylbenzene), capped (inlet adapter, three way stopcock), evacuated, back-filled (Ar), Et2O added, cooled (-78 °C), furan added, then iPrMgCl-LiCl/THF over 5 min added, stirred (-78°C, 30 min); quenched (satd. aq. NH4Cl), extd. (EtOAc), aq. layer extd. twice (EtOAc), combined organic layers washed (satd. aq. NaCl), dried over anhydrous Na2SO4, solvent removed under reduced pressure; purified by flash columnchromy.; detd. by (1)H NMR;
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 88 %; Overall yield = 31 mg; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 26
  • [ 4466-24-4 ]
  • [ 1245635-35-1 ]
  • [ 1245635-43-1 ]
  • [ 1245634-80-3 ]
YieldReaction ConditionsOperation in experiment
With (CH3)2CHMgCl-LiCl In tetrahydrofuran; diethyl ether pear-shaped flask charged (borylbenzene), capped (inlet adapter, three way stopcock), evacuated, back-filled (Ar), Et2O added, cooled (-78 °C), furan added, then iPrMgCl-LiCl/THF over 5 min added, stirred (-78°C, 30 min); quenched (satd. aq. NH4Cl), extd. (EtOAc), aq. layer extd. twice (EtOAc), combined organic layers washed (satd. aq. NaCl), dried over anhydrous Na2SO4, solvent removed under reduced pressure; purified by flash columnchromy.; detd. by (1)H NMR;
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 24 %; Overall yield = 5.1 mg; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 27
  • [ 4466-24-4 ]
  • [ 1245635-20-4 ]
  • [ 1245634-82-5 ]
  • [ 1245635-45-3 ]
YieldReaction ConditionsOperation in experiment
With (CH3)2CHMgCl-LiCl In tetrahydrofuran; diethyl ether pear-shaped flask charged with borylbenzene, capped (inlet adapter, three-way stopcock), evacuated, back-filled (Ar), anhydrous ether added, mixt. cooled (-78 °C), furan added, iPrMgCl-LiCl/THF added for 5 min. stirred (-78 °C, 30 min); mixt. quenched with saturated aq. NH4Cl, extd. (EtOAc), aq. layer extd. twice (EtOAc), combined organic layer washed (saturated aq. NaCl), driedover anhydrous Na2SO4, solvent removed (reduced pressure); flash column chromy.; detd. by (1)H NMR;
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 93 %; Overall yield = 47 mg; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 28
  • [ 4466-24-4 ]
  • [ 1245635-25-9 ]
  • [ 1245635-49-7 ]
  • [ 1245634-91-6 ]
YieldReaction ConditionsOperation in experiment
With (CH3)2CHMgCl-LiCl In tetrahydrofuran; diethyl ether pear-shaped flask charged with borylbenzene, capped (inlet adapter, three-way stopcock), evacuated, back-filled (Ar), anhydrous ether added, mixt. cooled (-78 °C), furan added, iPrMgCl-LiCl/THF added for 5 min. stirred (-78 °C, 30 min); mixt. quenched with saturated aq. NH4Cl, extd. (EtOAc), aq. layer extd. twice (EtOAc), combined organic layer washed (saturated aq. NaCl), driedover anhydrous Na2SO4, solvent removed (reduced pressure); column chrom y.; detd. by (1)H NMR;
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 64 %; Overall yield = 29 mg; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 29
  • [ 4466-24-4 ]
  • [ 1245635-30-6 ]
  • [ 1245635-50-0 ]
  • [ 1245634-92-7 ]
YieldReaction ConditionsOperation in experiment
With (CH3)2CHMgCl-LiCl In tetrahydrofuran; diethyl ether pear-shaped flask charged with borylbenzene, capped (inlet adapter, three-way stopcock), evacuated, back-filled (Ar), anhydrous ether added, mixt. cooled (-78 °C), furan added, iPrMgCl-LiCl/THF added for 5 min. stirred (-78 °C, 30 min); mixt. quenched with saturated aq. NH4Cl, extd. (EtOAc), aq. layer extd. twice (EtOAc), combined organic layer washed (saturated aq. NaCl), driedover anhydrous Na2SO4, solvent removed (reduced pressure); column chrom y.; detd. by (1)H NMR;
With isopropylmagnesium bromide In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 68 %; Overall yield = 29 mg; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 30
  • [ 4466-24-4 ]
  • [ 5332-24-1 ]
  • [ 925459-38-7 ]
YieldReaction ConditionsOperation in experiment
85% With PdCl(1,4-bis(diphenylphosphino)butane)(C<SUB>3</SUB>H<SUB>5</SUB>); potassium acetate In Diethyl carbonate at 140℃; for 23h; Inert atmosphere; regioselective reaction;
78% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
17% With [PdCl(C3H5)(dppb)]; potassium acetate at 150℃; for 24h; Inert atmosphere;
  • 31
  • [ 4466-24-4 ]
  • [ 623-00-7 ]
  • [ 925459-26-3 ]
YieldReaction ConditionsOperation in experiment
86% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
71% With palladium 10% on activated carbon; potassium acetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
61% With PdCl(1,4-bis(diphenylphosphino)butane)(C<SUB>3</SUB>H<SUB>5</SUB>); potassium acetate In Diethyl carbonate at 140℃; for 43h; Inert atmosphere; regioselective reaction;
57% With PdCl(C<SUB>3</SUB>H<SUB>5</SUB>)(1,4-bis(diphenylphosphino)butane); potassium acetate In dibutyl ether at 130℃; for 48h; Inert atmosphere;
15% With [PdCl(C3H5)(dppb)]; potassium acetate at 150℃; for 24h; Inert atmosphere;

  • 32
  • [ 4466-24-4 ]
  • [ 2042-37-7 ]
  • [ 1042318-52-4 ]
YieldReaction ConditionsOperation in experiment
88% With palladium 10% on activated carbon; potassium acetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
86% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
84% With PdCl(1,4-bis(diphenylphosphino)butane)(C<SUB>3</SUB>H<SUB>5</SUB>); potassium acetate In Diethyl carbonate at 140℃; for 43h; Inert atmosphere; regioselective reaction;
  • 33
  • [ 4466-24-4 ]
  • [ 99-90-1 ]
  • [ 925459-22-9 ]
YieldReaction ConditionsOperation in experiment
98% With dibromo[1-(cyclobutylmethyl)-3-(methoxyethyl)benzimidazole-2-ylidene]pyridine palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.5. General procedure for the arylation reaction General procedure: KOAc (1.0 mmol), aryl-bromide derivatives (1.0 mmol), heteroaryl derivatives (2-nbutylthiazole,2-n-butylthiophene and 2-n-butylfuran) (2.0 mmol) and Pd-NHC-PEPPSIcomplexes 2a-e (0.01 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL)in a small Schlenk tube under argon as described in literature [49]. The reaction mixturewas stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, andthe solvent was removed under vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluentto afford the pure product. The purity of the compounds was checked by gaschromatography (GC) and gas chromatography-mass spectrometry (GC-MS).Conversions were calculated by taking into account the conversion of aryl bromidesto products.
90% With bis[1-(1-methyl-2-dimethylaminoethyl)-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.3. General procedure for the direct C5 arylations General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pdcomplexes 2a-d (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a Schlenk tube equipped with a magnetic stirringbar. The Schlenk tube was purged several times with argon andwas placed in a preheated oil bath at 130 C. The reactants werestirred for 1 h with aryl bromides. The solvent was removed byheating the reaction vessel under vacuum. The products wereeluted by using an appropriate ratio of diethyl ether/pentane(1:3). The reaction mixture was purified by flash chromatographyon silica gel. The purity of compounds was checked by GC andNMR. Conversions were based on aryl bromides.
90% With potassium acetate; dibromo[1-{2-(4-hydroxyphenyl)ethyl}-3-(4-methylbenzyl)benzimidazole-2-ylidene]-3-chloropyridinepalladium(II) In N,N-dimethyl acetamide at 130℃; Inert atmosphere; Schlenk technique; 2.2. General procedure for Direct Arylation Reactions of Furan and Thiophene with Aryl Halides General procedure: The 2-n-butylfuran and 2-n-butylthiophene (1.5 mmol), the aryl halides (4-bromoacetophenone, 4-bromoanisole and 4- bromotoluene) (1 mmol), KOAc (1 mmol) and PEPPSI type Pd(II)NHC complexes (0.3 mol%) were dissolved in N,N - dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon gas as described in the literature [ 58 , 59 ]. The mix- ture was stirred at 130 °C for 2h. Then, the mixture was filtered through a short pad of celite, the solvents were evaporated under vacuum and the residue was dried in a vacuum. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
89% With N,N-dimethyl acetamide; dichloro[1-(N-phthalimidomethyl)-3-(2-morpholinoethyl)benzimidazol-2-ylidene](3-chloropyridine)palladium(II); potassium acetate at 110℃; for 1h; Inert atmosphere; Schlenk technique; General procedure for the arylation reaction General procedure: All catalytic reactions were carried out under an air atmosphere. The purchased reagents were used without further purifications for C-C bond forming reactions. In a typical reaction, 2-n-butylfuran or 2-n-butylthiophene (2 mmol), aryl bromides (1 mmol), KOAc (1 mmol), PEPPSI Pd-NHC (1 mol %) and N,N-dimethylacetamide (DMAc, 2 mL) were added to a dry 25 mL Schlenk tube. The mixture was then stirred for different times at different temperatures. After the reaction was finished, the solvent in the medium was removed completely by vacuum and the remaining solid in the Schlenk tube was dissolved in hexane/diethyl ether (5:1), before it was purified over silica gel. The chemical characterisations of the products were made by GC or GC-MS. The yields were calculated according to aryl bromides as internal references. The results are given in Table 1.
89% With potassium acetate; palladium diacetate; 2,3,5,6-tetrakis(N-4-methoxybenzylbenzimidazoliummethyl)benzene tetrabromide In N,N-dimethyl acetamide for 1h; Inert atmosphere; Schlenk technique; Heating; Green chemistry; General procedure for direct arylation of heteroaromatics General procedure: Under argon atmosphere, heteroaryl derivative (2-n-propylthiazole, 2-n-butylthiophene, 2-n-butylfuran and 4,5-dimethylthiazole) (2 mmol), 4-bromobenzene or 4-bromoacetophenone (1 mmol), KOAc (2 mmol), Pd(OAc)2 ( 0.005 mmol), 1a-1f (0.00125 mmol), DMAc (3 mL) were added into Schlenk tube. The mixture was stirred strongly at 130 oC for 1h. The solvent was removed under a vacuum. The product was eluted using a pentane-diethyl ether mixture (3:1). The reaction mixture was purified by flash chromatography on silica gel. GC yields were calculated relative to aryl bromide.
86% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
83% With bis[1,3-di(2,4,6-trimethoxybenzyl)perhydrobenzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction; General procedure for direct C5 arylations General procedure: The required heteroaryl derivative (2 mmol), aryl halide(1 mmol), Pd complex 3a-c (0.005 mmol), KOAc(1 mmol) and DMAc (2 mL) were placed in a Schlenk tube equipped with a magnetic stirring bar. The Schlenk tubewas purged several times with argon and then placed in apreheated oil bath at 130 C, and the reaction mixture was stirred for 1 h. The mixture was analyzed by gas chromatographyto determine the conversion of the aryl bromide and the yield of product. The solvent was removed byheating the reaction vessel under vacuum, and the residuewas charged directly onto a silica gel column. The productswere eluted using diethyl ether/pentane (1:3).
83% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
82% With palladium 10% on activated carbon; potassium acetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
70% With PdCl(1,4-bis(diphenylphosphino)butane)(C<SUB>3</SUB>H<SUB>5</SUB>); potassium acetate In Diethyl carbonate at 140℃; for 72h; Inert atmosphere; regioselective reaction;
With bis[1-phenyl-3-(phthalimido-N-propyl)benzimidazol-2-ylidene]dibromopalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 9 2-Phenyl-5-n-butylthiophene (9) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
With bis[1-(2-morpholinoethyl)-3-naphthalenomethylbenzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction;
With 1-naphthalenomethyl-3-benzylbenzimidazol-2-ylidene-N-(3-chloropyridine)dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction; General method for direct arylation General procedure: Heteroaryl derivative (2-n-butylfuran, 2-n-butylthiophene and2-n-propylthiazole) (2 mmol), aryl bromide (p-bromoacetophenone,p-bromoanisole, p-bromotoluene and bromobenzene)(1 mmol), PEPPSI Pd-NHC complexes 2a-f (0.003 mmol), KOAc(1 mmol) and N,N-dimethylacetamide (DMAc) (2 mL) were addedto a small Schlenk tube equipped with a magnetic stirring bar asdescribed in the literature [20-22]. The Schlenk tube was heatedin an oil bath at 130 C for 1 h. When the reaction was completed,the solvent in the reaction media was removed by heating thereaction vessel under vacuum. Then, the pentane and diethylether mixture (3:1) was added to the reaction ambient. As aresult of this process, the obtained product was purified by usingflash chromatography on silica gel. The purity of the compoundwas checked by GC and NMR. Conversions were based on arylbromides.
With bis[1-benzyl-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; 2.7 General Method forDirect Arylation ofFuranandThiophene withAryl Bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone,4-bromoanisole and 4-bromo toluene) (1mmol) and heteroarylderivatives (2-n-butylfuran and 2-n-butylthiophene)(2 mmol), KOAc (1 mmol) and bis-(NHC)Pd(II) complexes1a-f (0.003mmol) were dissolved in N,N-dimethylacetamide(DMAc) (2mL) in a small Schlenk tube underargon as described in the literature [46]. The reaction mixturewas stirred in an oil bath at 130 °C for 1h then wascooled to room temperature and the solvent was removedunder vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by usingdiethyl ether/n-hexane (1:5) as eluent to afford the pureproduct. The purity of the compounds was checked bygas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated bytaking into account the conversion of aryl bromides toproducts.
With bis[1-(2-ethoxyethyl)-3-(4-vinylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; General method for direct arylation of furan and thiophene with aryl bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1mmol) and heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), KOAc (1 mmol) and bis(NHC)-Pd(II) complexes 1a-i (0.003mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2mL) in a small Schlenk tube under argon as described in the literature [22]. The reaction mixture was stirred in an oil bath at 130°C for 1h. Then was cooled to room temperature and the solvent was removed under vacuum. The obtained residue was purified by column chromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
With C56H42Cl2N6O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; Procedure for arylation of furan, thiophene and thiazole General procedure: The heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), the aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1 mmol), KOAc (1 mmol) and bis-(NHC)PdX2 complexes 1a-i (0.003 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon as described in the literature [31]. The mixture was stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, and the solvent was removed under vacuum. The residue was purified by column chromatography (silica gel 60-120 mesh) using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purities of the compounds were checked by GC and GC-MS. Conversions were calculated based on the aryl bromide.
With C40H44Br2N4O6Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique;

Reference: [1]Şahin, Neslihan; Serdaroğlu, Goncagül; Düşünceli, Serpil Demir; Tahir, Muhammad Navaz; Arıcı, Cengiz; Özdemir, İsmail [Journal of Coordination Chemistry, 2019, vol. 72, # 19-21, p. 3258 - 3284]
[2]Yiğit, Murat; Yiğit, Beyhan; Gök, Yetkin [Inorganica Chimica Acta, 2016, vol. 453, p. 23 - 28]
[3]Çağlılar, Tuba; Aktaş, Aydın; Aygün, Muhittin; Behçet, Ayten; Celepci, Duygu Barut; Gök, Yetkin [Journal of Molecular Structure, 2021, vol. 1246]
[4]Akkoç, Senem; Gök, Yetkin; Ilhan, Ilhan Özer; Kayser, Veysel [Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 81 - 88]
[5]Özdemir, İsmail; Ulu, Öznur Doğan [Arkivoc, 2021, vol. 2021, # 8, p. 286 - 295]
[6]Location in patent: experimental part Dong, Jia Jia; Roger, Julien; Pogan, Franc; Doucet, Henri [Green Chemistry, 2009, vol. 11, # 11, p. 1832 - 1846]
[7]Yiğit, Beyhan; Yiğit, Murat; Dağdeviren, Zeynep; Özdemir, İsmail [Transition Metal Chemistry, 2016, vol. 41, # 7, p. 751 - 757]
[8]Kaloğlu, Murat; Özdemir, İsmail [Applied Organometallic Chemistry, 2018, vol. 32, # 7]
[9]Mao, Shuxin; Shi, Xinzhe; Soulé, Jean-François; Doucet, Henri [Advanced Synthesis and Catalysis, 2018, vol. 360, # 17, p. 3306 - 3317]
[10]Location in patent: experimental part Dong, Jia Jia; Roger, Julien; Verrier, Cecile; Martin, Thibaut; Le Goff, Ronan; Hoarau, Christophe; Doucet, Henri [Green Chemistry, 2010, vol. 12, # 11, p. 2053 - 2063]
[11]Akkoç, Senem; Gök, Yetkin; Akkurt, Mehmet; Tahir, Muhammad Nawaz [Inorganica Chimica Acta, 2014, vol. 413, p. 221 - 230]
[12]Akkoc, Senem; Gök, Yetkin [Applied Organometallic Chemistry, 2014, vol. 28, # 12, p. 854 - 860]
[13]Akkoç, Senem; Gök, Yetkin [Inorganica Chimica Acta, 2015, vol. 429, p. 34 - 38]
[14]Sarı, Yakup; Aktaş, Aydın; Barut Celepci, Duygu; Gök, Yetkin; Aygün, Muhittin [Catalysis Letters, 2017, vol. 147, # 9, p. 2340 - 2351]
[15]Gök, Yetkin; Aktaş, Aydın; Erdoğan, Hülya; Sarı, Yakup [Inorganica Chimica Acta, 2018, vol. 471, p. 735 - 740]
[16]Erdoğan, Hülya; Aktaş, Aydın; Gök, Yetkin; Sarı, Yakup [Transition Metal Chemistry, 2018, vol. 43, # 1, p. 31 - 37]
[17]Gök, Yetkin; Aktaş, Aydın; Sarı, Yakup; Erdoğan, Hülya [Journal of the Iranian Chemical Society, 2019, vol. 16, # 2, p. 423 - 433]
  • 34
  • [ 4466-24-4 ]
  • [ 104-92-7 ]
  • 2-n-butyl-5-(4-methoxyphenyl)-furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With potassium acetate; dibromo[1-{2-(4-hydroxyphenyl)ethyl}-3-(2,4,6-trimethylbenzyl) benzimidazole-2-ylidene]-3-chloropyridinepalladium(II) In N,N-dimethyl acetamide at 130℃; Inert atmosphere; Schlenk technique; 2.2. General procedure for Direct Arylation Reactions of Furan and Thiophene with Aryl Halides General procedure: The 2-n-butylfuran and 2-n-butylthiophene (1.5 mmol), the aryl halides (4-bromoacetophenone, 4-bromoanisole and 4- bromotoluene) (1 mmol), KOAc (1 mmol) and PEPPSI type Pd(II)NHC complexes (0.3 mol%) were dissolved in N,N - dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon gas as described in the literature [ 58 , 59 ]. The mix- ture was stirred at 130 °C for 2h. Then, the mixture was filtered through a short pad of celite, the solvents were evaporated under vacuum and the residue was dried in a vacuum. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
87% With bis[1-(1-methyl-2-dimethylaminoethyl)-3-(2,4,6-trimethylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.3. General procedure for the direct C5 arylations General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pdcomplexes 2a-d (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a Schlenk tube equipped with a magnetic stirringbar. The Schlenk tube was purged several times with argon andwas placed in a preheated oil bath at 130 C. The reactants werestirred for 1 h with aryl bromides. The solvent was removed byheating the reaction vessel under vacuum. The products wereeluted by using an appropriate ratio of diethyl ether/pentane(1:3). The reaction mixture was purified by flash chromatographyon silica gel. The purity of compounds was checked by GC andNMR. Conversions were based on aryl bromides.
79% With bis[1,3-bis(2-phenylethyl)benzimidazol-2-ylidene]dichloridopalladium(II); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
78% With bis[1,3-di(2,4,6-trimethoxybenzyl)perhydrobenzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction; General procedure for direct C5 arylations General procedure: The required heteroaryl derivative (2 mmol), aryl halide(1 mmol), Pd complex 3a-c (0.005 mmol), KOAc(1 mmol) and DMAc (2 mL) were placed in a Schlenk tube equipped with a magnetic stirring bar. The Schlenk tubewas purged several times with argon and then placed in apreheated oil bath at 130 C, and the reaction mixture was stirred for 1 h. The mixture was analyzed by gas chromatographyto determine the conversion of the aryl bromide and the yield of product. The solvent was removed byheating the reaction vessel under vacuum, and the residuewas charged directly onto a silica gel column. The productswere eluted using diethyl ether/pentane (1:3).
57% With dibromo[1-(cyclobutylmethyl)-3-(methoxyethyl)benzimidazole-2-ylidene]pyridine palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.5. General procedure for the arylation reaction General procedure: KOAc (1.0 mmol), aryl-bromide derivatives (1.0 mmol), heteroaryl derivatives (2-nbutylthiazole,2-n-butylthiophene and 2-n-butylfuran) (2.0 mmol) and Pd-NHC-PEPPSIcomplexes 2a-e (0.01 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL)in a small Schlenk tube under argon as described in literature [49]. The reaction mixturewas stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, andthe solvent was removed under vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluentto afford the pure product. The purity of the compounds was checked by gaschromatography (GC) and gas chromatography-mass spectrometry (GC-MS).Conversions were calculated by taking into account the conversion of aryl bromidesto products.
55% With tetrabutylammomium bromide; potassium acetate; palladium dichloride; tricyclohexylphosphine In N,N-dimethyl acetamide at 110℃; for 16h; Inert atmosphere; Glovebox; Schlenk technique;
18% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
With bis[1-phenyl-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 10 2-n-Butyl-5-acetophenylfuran (10) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
With bis[1-(2-morpholinoethyl)-3-(2-methylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction;
With 1-naphthalenomethyl-3-(4-methylbenzyl)benzimidazol-2-ylidene-N-(3-chloropyridine)dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction; General method for direct arylation General procedure: Heteroaryl derivative (2-n-butylfuran, 2-n-butylthiophene and2-n-propylthiazole) (2 mmol), aryl bromide (p-bromoacetophenone,p-bromoanisole, p-bromotoluene and bromobenzene)(1 mmol), PEPPSI Pd-NHC complexes 2a-f (0.003 mmol), KOAc(1 mmol) and N,N-dimethylacetamide (DMAc) (2 mL) were addedto a small Schlenk tube equipped with a magnetic stirring bar asdescribed in the literature [20-22]. The Schlenk tube was heatedin an oil bath at 130 C for 1 h. When the reaction was completed,the solvent in the reaction media was removed by heating thereaction vessel under vacuum. Then, the pentane and diethylether mixture (3:1) was added to the reaction ambient. As aresult of this process, the obtained product was purified by usingflash chromatography on silica gel. The purity of the compoundwas checked by GC and NMR. Conversions were based on arylbromides.
With bis[1-(4-methylbenzyl)-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; 2.7 General Method forDirect Arylation ofFuranandThiophene withAryl Bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone,4-bromoanisole and 4-bromo toluene) (1mmol) and heteroarylderivatives (2-n-butylfuran and 2-n-butylthiophene)(2 mmol), KOAc (1 mmol) and bis-(NHC)Pd(II) complexes1a-f (0.003mmol) were dissolved in N,N-dimethylacetamide(DMAc) (2mL) in a small Schlenk tube underargon as described in the literature [46]. The reaction mixturewas stirred in an oil bath at 130 °C for 1h then wascooled to room temperature and the solvent was removedunder vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by usingdiethyl ether/n-hexane (1:5) as eluent to afford the pureproduct. The purity of the compounds was checked bygas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated bytaking into account the conversion of aryl bromides toproducts.
With bis[1-(2,3,5,6-tetramethylbenzyl)-3-(4-vinylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; General method for direct arylation of furan and thiophene with aryl bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1mmol) and heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), KOAc (1 mmol) and bis(NHC)-Pd(II) complexes 1a-i (0.003mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2mL) in a small Schlenk tube under argon as described in the literature [22]. The reaction mixture was stirred in an oil bath at 130°C for 1h. Then was cooled to room temperature and the solvent was removed under vacuum. The obtained residue was purified by column chromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
With C40H38Br2N6O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; Procedure for arylation of furan, thiophene and thiazole General procedure: The heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), the aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1 mmol), KOAc (1 mmol) and bis-(NHC)PdX2 complexes 1a-i (0.003 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon as described in the literature [31]. The mixture was stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, and the solvent was removed under vacuum. The residue was purified by column chromatography (silica gel 60-120 mesh) using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purities of the compounds were checked by GC and GC-MS. Conversions were calculated based on the aryl bromide.
With C46H40Cl2N4O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique;

Reference: [1]Çağlılar, Tuba; Aktaş, Aydın; Aygün, Muhittin; Behçet, Ayten; Celepci, Duygu Barut; Gök, Yetkin [Journal of Molecular Structure, 2021, vol. 1246]
[2]Yiğit, Murat; Yiğit, Beyhan; Gök, Yetkin [Inorganica Chimica Acta, 2016, vol. 453, p. 23 - 28]
[3]Location in patent: experimental part Ozdemir, Ismail; Goek, Yetkin; Oezeroglu, Oezlem; Kaloglu, Murat; Doucet, Henri; Bruneau, Christian [European Journal of Inorganic Chemistry, 2010, # 12, p. 1798 - 1805]
[4]Yiğit, Beyhan; Yiğit, Murat; Dağdeviren, Zeynep; Özdemir, İsmail [Transition Metal Chemistry, 2016, vol. 41, # 7, p. 751 - 757]
[5]Şahin, Neslihan; Serdaroğlu, Goncagül; Düşünceli, Serpil Demir; Tahir, Muhammad Navaz; Arıcı, Cengiz; Özdemir, İsmail [Journal of Coordination Chemistry, 2019, vol. 72, # 19-21, p. 3258 - 3284]
[6]Wysocki, Jedrzej; Ortega, Nuria; Glorius, Frank [Angewandte Chemie - International Edition, 2014, vol. 53, # 33, p. 8751 - 8755][Angew. Chem., 2014, vol. 126, # 33, p. 8896 - 8900]
[7]Location in patent: experimental part Dong, Jia Jia; Roger, Julien; Pogan, Franc; Doucet, Henri [Green Chemistry, 2009, vol. 11, # 11, p. 1832 - 1846]
[8]Akkoç, Senem; Gök, Yetkin; Akkurt, Mehmet; Tahir, Muhammad Nawaz [Inorganica Chimica Acta, 2014, vol. 413, p. 221 - 230]
[9]Akkoc, Senem; Gök, Yetkin [Applied Organometallic Chemistry, 2014, vol. 28, # 12, p. 854 - 860]
[10]Akkoç, Senem; Gök, Yetkin [Inorganica Chimica Acta, 2015, vol. 429, p. 34 - 38]
[11]Sarı, Yakup; Aktaş, Aydın; Barut Celepci, Duygu; Gök, Yetkin; Aygün, Muhittin [Catalysis Letters, 2017, vol. 147, # 9, p. 2340 - 2351]
[12]Gök, Yetkin; Aktaş, Aydın; Erdoğan, Hülya; Sarı, Yakup [Inorganica Chimica Acta, 2018, vol. 471, p. 735 - 740]
[13]Erdoğan, Hülya; Aktaş, Aydın; Gök, Yetkin; Sarı, Yakup [Transition Metal Chemistry, 2018, vol. 43, # 1, p. 31 - 37]
[14]Gök, Yetkin; Aktaş, Aydın; Sarı, Yakup; Erdoğan, Hülya [Journal of the Iranian Chemical Society, 2019, vol. 16, # 2, p. 423 - 433]
  • 35
  • [ 4466-24-4 ]
  • [ 95-46-5 ]
  • [ 1159850-56-2 ]
YieldReaction ConditionsOperation in experiment
80% With 1-diphenylphosphino-2-diphenylphosphino-4-tert-butyl-cyclopentadienyl-1'-diisopropylphosphino-3'-tert-butyl-cyclopentadienyliron; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
41% With bis[1,3-bis(2-phenylethyl)benzimidazol-2-ylidene]dichloridopalladium(II); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
16% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
  • 36
  • [ 4466-24-4 ]
  • [ 392-83-6 ]
  • [ 925459-32-1 ]
YieldReaction ConditionsOperation in experiment
90% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
90% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; Inert atmosphere;
  • 37
  • [ 4466-24-4 ]
  • [ 1122-91-4 ]
  • [ 925459-24-1 ]
YieldReaction ConditionsOperation in experiment
100% With dibromo[1-(cyclobutylmethyl)-3-(4-methoxybenzyl)benzimidazole-2-ylidene]-pyridine palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.5. General procedure for the arylation reaction General procedure: KOAc (1.0 mmol), aryl-bromide derivatives (1.0 mmol), heteroaryl derivatives (2-nbutylthiazole,2-n-butylthiophene and 2-n-butylfuran) (2.0 mmol) and Pd-NHC-PEPPSIcomplexes 2a-e (0.01 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL)in a small Schlenk tube under argon as described in literature [49]. The reaction mixturewas stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, andthe solvent was removed under vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluentto afford the pure product. The purity of the compounds was checked by gaschromatography (GC) and gas chromatography-mass spectrometry (GC-MS).Conversions were calculated by taking into account the conversion of aryl bromidesto products.
91% With potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
75% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
  • 38
  • [ 4466-24-4 ]
  • [ 1276113-16-6 ]
  • [ 1276113-21-3 ]
YieldReaction ConditionsOperation in experiment
86% With 18-crown-6 ether; Nonafluorobutanesulfonyl fluoride; caesium carbonate In acetonitrile at 60℃; for 29h; Inert atmosphere;
  • 39
  • [ 4466-24-4 ]
  • [ 232611-15-3 ]
  • [ 1276113-22-4 ]
YieldReaction ConditionsOperation in experiment
72% With 18-crown-6 ether; Nonafluorobutanesulfonyl fluoride; caesium carbonate In acetonitrile at 60℃; for 5h; Inert atmosphere;
  • 40
  • [ 4466-24-4 ]
  • [ 1276113-18-8 ]
  • [ 1276113-24-6 ]
  • [ 1276113-25-7 ]
YieldReaction ConditionsOperation in experiment
1: 67% 2: 25% Stage #1: 2-Butylfuran; 4-(1,3-dioxolan-2-yl)-2,6-bis(trimethylsilyl)phenol With 18-crown-6 ether; Nonafluorobutanesulfonyl fluoride; sodium hydride In acetonitrile at 60℃; for 2h; Inert atmosphere; Stage #2: With caesium carbonate In acetonitrile for 9h; Reflux;
  • 41
  • [ 4466-24-4 ]
  • [ 15288-53-6 ]
  • [ 1276113-20-2 ]
YieldReaction ConditionsOperation in experiment
86% With 18-crown-6 ether; Nonafluorobutanesulfonyl fluoride; caesium carbonate In acetonitrile at 60℃; for 7.5h; Inert atmosphere;
  • 42
  • [ 4466-24-4 ]
  • [ 586-77-6 ]
  • [ 1236844-79-3 ]
YieldReaction ConditionsOperation in experiment
69% With bis[1,3-bis(2-phenylethyl)benzimidazol-2-ylidene]dichloridopalladium(II); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere;
44% With 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenylmethyl)ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
  • 43
  • [ 4466-24-4 ]
  • [ 5216-17-1 ]
  • [ 1322575-32-5 ]
  • 44
  • [ 4466-24-4 ]
  • [ 1385058-12-7 ]
  • [ 1385058-18-3 ]
  • [ 1385058-23-0 ]
YieldReaction ConditionsOperation in experiment
With n-butyllithium In hexane; toluene at -78℃; for 0.25h; Inert atmosphere; regioselective reaction; General procedure for generation of 6,7-benzofuranyne and Diels-Alder trapping General procedure: In a flame-dried 50 mL round-bottom flask, 75 mg (0.272 mmol) 6,7-dibromobenzofuran and 338 mg (2.72 mmol) 2-tert-butylfuran were dissolved in 10 mL dry toluene under argon. This solution was cooled to -78 oC, then 0.13 mL (0.3264 mmol) n-butyllithium (2.5 M in hexanes) was added dropwise via syringe. The solution was stirred at -78 oC for 15 minutes, then allowed to warm to room temperature. The reaction was quenched by addition of 10 mL water, and the phases were separated. The aqueous phase was washed with 2 x 10 mL ether. The combined organic phase was washed with brine (10 mL), dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The crude residue was then subjected to flash chromatography using a gradient of ethyl acetate in hexanes (1% to 5%) to give the cycloadduct as a mixture of regioisomers 16a and 16b (HRMS was carried out on the mixture of isomers to give positive identification). The mixture of regioisomers could then be resolved using column chromatography, eluting with a gradient of tert-butyl methyl ether in pentane (0.5% to 2.5%).
  • 45
  • [ 4466-24-4 ]
  • [ 38940-62-4 ]
  • [ 1393709-33-5 ]
YieldReaction ConditionsOperation in experiment
89% With PdCl(C3H5)(dppb); potassium acetate; In N,N-dimethyl acetamide; at 150℃; for 20h;Inert atmosphere; In a typical experiment, the bromopyridine (1 mmol), heteroaromatic derivative (2 mmol), KOAc (0.196 g, 2 mmol) and PdCl(C3H5)(dppb) (6.8 mg, 0.01 mmol), were dissolved in DMAc (4 mL) under an argon atmosphere. The reaction mixture was stirred at 100 C or 150 C (see schemes) for 20 h. After evaporation of the solvent, the product was purified by silica gel column chromatography.
  • 46
  • [ 4466-24-4 ]
  • [ 35590-37-5 ]
  • [ 1393709-43-7 ]
YieldReaction ConditionsOperation in experiment
74% With PdCl(C3H5)(dppb); potassium acetate In N,N-dimethyl acetamide at 150℃; for 20h; Inert atmosphere; regioselective reaction; 3.3. General procedure In a typical experiment, the bromopyridine (1 mmol), heteroaromatic derivative (2 mmol), KOAc (0.196 g, 2 mmol) and PdCl(C3H5)(dppb) (6.8 mg, 0.01 mmol), were dissolved in DMAc (4 mL) under an argon atmosphere. The reaction mixture was stirred at 100 °C or 150 °C (see schemes) for 20 h. After evaporation of the solvent, the product was purified by silica gel column chromatography.
  • 47
  • [ 4466-24-4 ]
  • [ 1401352-39-3 ]
YieldReaction ConditionsOperation in experiment
85% With 12-molybdosilicic acid; bis(acetylacetonato)palladium(II) In dimethyl sulfoxide at 30℃; for 20h;
80% With oxygen; palladium diacetate; trifluoroacetic acid In dimethyl sulfoxide at 50℃; Sealed tube; regioselective reaction;
58% With silver hexafluoroantimonate; copper(II) 2-ethylhexanoate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; cesium pivalate In tert-Amyl alcohol at 120℃; Inert atmosphere;
  • 48
  • [ 4466-24-4 ]
  • [ 5380-42-7 ]
  • [ 1401352-30-4 ]
YieldReaction ConditionsOperation in experiment
81% With silver hexafluoroantimonate; copper(II) 2-ethylhexanoate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; cesium pivalate In tert-Amyl alcohol at 120℃; Inert atmosphere;
49% With 1,10-Phenanthroline; palladium(II) trifluoroacetate; silver(I) acetate In N,N-dimethyl acetamide; dimethyl sulfoxide at 100℃; for 8h;
  • 49
  • [ 4466-24-4 ]
  • [ 58861-48-6 ]
  • [ 1401352-26-8 ]
  • 50
  • [ 4466-24-4 ]
  • [ 99-91-2 ]
  • [ 925459-22-9 ]
YieldReaction ConditionsOperation in experiment
80% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 20h; Inert atmosphere; Schlenk technique;
48% With C36H50Cl2N3OPPd; potassium carbonate; trimethylpyruvic acid In N,N-dimethyl acetamide at 110℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;
With bis[1-phenyl-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 20h; Schlenk technique; Inert atmosphere; 15 2-n-Butyl-5-(4-methylphenyl)thiophene (15) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
With C50H44Cl2N4O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 16h; Inert atmosphere; Schlenk technique;
With dichlorobis[1-benzyl-3-(2-hydroxyethyl)benzimidazol-2-ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Green chemistry; 2.1j General method for direct arylation of 2-nbutylfuranand 2-n-butylthiophene with arylhalides General procedure: The derivatives of heteroaryl (2-n-butylfuranand 2-n-butylthiophene) (2 mmol), the derivatives of arylchloride/bromide (4-chloroacetophenone, 4-chloroanisole,4-bromoacetophenone, 4-bromoanisole) (1 mmol), KOAc(1 mmol) and the N-coordinate-Pd(II)(NHC) complexes 1a-b or bis(NHC)Pd(II) complexes 2a-g (0.3% mmol) weredissolved in N,N-dimethylacetamide (DMAc) (2 mL) in asmall Schlenk tube as described in the literature.42,43,52 Thereaction mixture was stirred in an oil bath at 130 °C for 1h/16 h. The solvent was removed under vacuum. Themixture was purified by using the column chromatography(silica gel 60-120 mesh) with ethylacetat/n-hexane (1:5) aseluent to obtain the pure product. The purity of the compounds was checked by gas chromatography (GC). Theconversions were calculated by taking into account theconversion of the aryl bromides to the products.

  • 51
  • [ 4466-24-4 ]
  • [ 108-41-8 ]
  • [ 1351438-70-4 ]
YieldReaction ConditionsOperation in experiment
71% With C36H50Cl2N3OPPd; potassium carbonate; trimethylpyruvic acid In N,N-dimethyl acetamide at 110℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;
  • 52
  • [ 4466-24-4 ]
  • [ 6781-98-2 ]
  • [ 1313012-83-7 ]
YieldReaction ConditionsOperation in experiment
84% With C36H50Cl2N3OPPd; potassium carbonate; trimethylpyruvic acid In N,N-dimethyl acetamide at 110℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;
  • 53
  • [ 4466-24-4 ]
  • [ 93-55-0 ]
  • [ 1440662-68-9 ]
YieldReaction ConditionsOperation in experiment
64% With silver (II) carbonate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; lithium acetate; palladium diacetate; tricyclohexylphosphine In 1,2-dimethoxyethane at 100℃; for 24h; Schlenk technique; Inert atmosphere; (E)-3-(5-butylfuran-2-yl)-1-phenyl-2-propen-1-one General procedure: In a glove box, a 25 mL of Schlenk tube equipped with a stir bar was charged with Pd(OAc)2 (0.03 mmol, 0.1 equiv), PCy3 (0.03 or 0.06 mmol, 0.1 or 0.2 equiv), LiOAc (0.45 mmol, 1.5 equiv) (or NaOAc), TEMPO (0.12 mmol, 0.4 equiv), Ag2CO3 (0.9 mmol, 3 equiv). The tube was fitted with a rubber septum and removed out of the glove box. DME (2 mL), propiophenone (0.9 mmol, 3.0 equiv) and thiophene (0.3 mmol, 1.0 equiv) were added in turn to the Schlenk tube through the rubber septum using syringes, and then the septum was replaced with a Teflon screwcap under nitrogen flow (if the thiophene or the substituted propiophenone was solid, it was added to the tube in the glove box). The reaction mixture was stirred at 100 oC or 120 oC for 24 h. After cooling down, the reaction mixture was diluted with 10 mL of ethyl ether, filtered through a pad of silica gel, followed by washing the pad of the silica gel with the same solvent (20 mL), concentrated under reduced pressure. The residue was then purified by flash chromatography on silica gel with 2-15 % ethyl ether in petroleum ether as eluent to provide the corresponding product.
  • 54
  • [ 4466-24-4 ]
  • [ 133739-70-5 ]
  • [ 1426829-18-6 ]
  • 55
  • [ 4466-24-4 ]
  • [ 1559-88-2 ]
  • [ 1426829-11-9 ]
  • 56
  • [ 4466-24-4 ]
  • [ 1245635-40-8 ]
  • [ 1245634-82-5 ]
  • [ 1245635-45-3 ]
YieldReaction ConditionsOperation in experiment
With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.333333h; Inert atmosphere; Overall yield = 67 %; Overall yield = 29 mg; regioselective reaction; General procedure for the generation of 11 followed by its Diels-Alder reaction with furans 6 General procedure: An oven-dried pear-shaped flask was charged with a precursor (5A or 5B) (1.0 equiv) and capped with an inlet adapter with a three-way stopcock. The flask was evacuated and back-filled with argon. An anhydrous solvent (0.10 M) was added, and the reaction mixture was cooled to -78 ºC. A furan 6 (10 equiv) was added, and a solution of BuLi [n-BuLi or s-BuLi (each 1.2 equiv) or t-BuLi (2.2 equiv)] was slowly added over 5 min. After being stirred at -78 ºC for 15 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude product was purified by flash column chromatography to afford the product (16 and 22). The analytical data of the products were in good agreement with those in the mail text of this manuscript.
  • 57
  • [ 4466-24-4 ]
  • [ 1431330-17-4 ]
  • [ 1245635-43-1 ]
  • [ 1245634-80-3 ]
YieldReaction ConditionsOperation in experiment
With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.333333h; Inert atmosphere; Overall yield = 52 %; Overall yield = 27 mg; regioselective reaction; General procedure for the generation of 11 followed by its Diels-Alder reaction with furans 6 General procedure: An oven-dried pear-shaped flask was charged with a precursor (5A or 5B) (1.0 equiv) and capped with an inlet adapter with a three-way stopcock. The flask was evacuated and back-filled with argon. An anhydrous solvent (0.10 M) was added, and the reaction mixture was cooled to -78 ºC. A furan 6 (10 equiv) was added, and a solution of BuLi [n-BuLi or s-BuLi (each 1.2 equiv) or t-BuLi (2.2 equiv)] was slowly added over 5 min. After being stirred at -78 ºC for 15 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude product was purified by flash column chromatography to afford the product (16 and 22). The analytical data of the products were in good agreement with those in the mail text of this manuscript.
  • 58
  • [ 4466-24-4 ]
  • [ 1431330-18-5 ]
  • [ 1245635-43-1 ]
  • [ 1245634-80-3 ]
YieldReaction ConditionsOperation in experiment
With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.333333h; Inert atmosphere; Overall yield = 51 %; Overall yield = 23 mg; regioselective reaction; General procedure for the generation of 11 followed by its Diels-Alder reaction with furans 6 General procedure: An oven-dried pear-shaped flask was charged with a precursor (5A or 5B) (1.0 equiv) and capped with an inlet adapter with a three-way stopcock. The flask was evacuated and back-filled with argon. An anhydrous solvent (0.10 M) was added, and the reaction mixture was cooled to -78 ºC. A furan 6 (10 equiv) was added, and a solution of BuLi [n-BuLi or s-BuLi (each 1.2 equiv) or t-BuLi (2.2 equiv)] was slowly added over 5 min. After being stirred at -78 ºC for 15 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude product was purified by flash column chromatography to afford the product (16 and 22). The analytical data of the products were in good agreement with those in the mail text of this manuscript.
  • 59
  • [ 4466-24-4 ]
  • [ 1245635-09-9 ]
  • [ 1245635-10-2 ]
  • [ 1245635-11-3 ]
YieldReaction ConditionsOperation in experiment
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; Overall yield = 71 %; Overall yield = 35 mg; 5-(t-Butyl)-1-butyl-7-methyl-1,4-dihydro-1,4-epoxynaphthalene (distal-13Bb) and 8-(t-butyl)-1-butyl-6-methyl-1,4-dihydro-1,4-epoxynaphthalene (proximal-13Bb ) An oven-dried pear-shaped flask was charged with precursor 51 (76 mg, 0.18 mmol) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (1.8 mL) was added, and then the reaction mixture was cooled to -78 ºC. 2-n-Butylfuran 6b (80 μL, 0.56 mmol) was added, and then i-PrMgCl·LiCl [1.3 M in THF (0.17 mL, 0.22 mmol)] was slowly added over 5 min. After being stirred at -78 ºC for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution, and was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution, and was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure. The crude product (distal/proximal = 52 : 48) was purified by flash column chromatography (hexane) to afford a hardly separable mixture of distal-13Bb and proximal-13Bb (35 mg, 71%).
  • 60
  • [ 4466-24-4 ]
  • [ 1426579-75-0 ]
  • [ 1245634-82-5 ]
  • [ 1245635-45-3 ]
YieldReaction ConditionsOperation in experiment
With TurboGrignard In tetrahydrofuran at -78 - 0℃; for 0.583333h; Inert atmosphere; Overall yield = 74 %Spectr.; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 61
  • [ 4466-24-4 ]
  • [ 1426579-80-7 ]
  • [ 1245634-82-5 ]
  • [ 1245635-45-3 ]
YieldReaction ConditionsOperation in experiment
With TurboGrignard In tetrahydrofuran at -78 - 0℃; for 0.583333h; Inert atmosphere; Overall yield = 74 %Spectr.; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 62
  • [ 4466-24-4 ]
  • [ 1431330-26-5 ]
  • C20H27BO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
49 %Spectr. With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 63
  • [ 4466-24-4 ]
  • [ 1431330-27-6 ]
  • C20H25BO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
49 %Spectr. With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 64
  • [ 4466-24-4 ]
  • [ 1431330-28-7 ]
  • C17H21BO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 65
  • [ 4466-24-4 ]
  • [ 1431330-29-8 ]
  • C15H19BO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With TurboGrignard In tetrahydrofuran; diethyl ether at -78℃; for 0.583333h; Inert atmosphere; regioselective reaction; 4.2 General procedure for the generation of borylbenzyne 11 followed by its Diels-Alder reaction with furan 6 or pyrrol 41 (Tables 4-8) General procedure: An oven-dried pear-shaped flask was charged with a borylbenzyne precursor 28 (1.0 equiv) and capped with an inlet adapter with a three-way stopcock and then evacuated and back-filled with argon. Anhydrous Et2O (0.10 M) was added, and the reaction mixture was cooled to -78 °C. Furan 6 or pyrrol 41 (3.0 equiv) was added, and then a 1.3 M solutions of i-PrMgCl·LiCl (1.2 equiv) in THF was slowly added over 5 min. After being stirred at -78 °C for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution. The reaction mixture was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc. The combined organic layer was washed with a saturated aqueous NaCl solution and dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel. Most of major regioisomers (distal-16 and distal-42) were isolated, while minor regioisomers (proximal-16 and proximal-42) could be hardly isolated because both distal and proximal adducts were slightly prone to be adsorbed on silica gel. The structures of the minor regioisomers were determined by similarity of their characteristic 1H NMR data to those of proximal-16Ab, whose structure was determined by NOESY spectra.
  • 66
  • [ 4466-24-4 ]
  • [ 1431330-25-4 ]
  • [ 1245634-82-5 ]
YieldReaction ConditionsOperation in experiment
19% With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.583333h; Inert atmosphere; General procedure for the reaction of ref. 15 General procedure: An oven-dried pear-shaped flask was charged with a precursor I-III (1.0 equiv) and capped with an inlet adapter with a three-way stopcock. The flask was evacuated and back-filled with argon. Anhydrous THF (0.10 M) was added, and the reaction mixture was cooled to -78 ºC. A furan 6b (10 equiv) was added, and a solution of LDA (1.2 equiv) in THF or a solution of n-BuLi (1.2 equiv) in hexane was slowly added over 5 min. After being stirred at -78 ºC for 30 min, the reaction mixture was quenched by a saturated aqueous NH4Cl solution and was extracted with EtOAc. Aqueous layer was extracted twice with EtOAc, and the combined organic layer was washed with a saturated aqueous NaCl solution. The organic layer was dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude product was subjected to 1H NMR analysis and also purified by flash column chromatography to afford 16Ab (for entry 1).
  • 67
  • [ 4466-24-4 ]
  • (3S*,4R*)-2-chloro-3,4-bis((trimethylsilyl)methyl)-cyclopentanone [ No CAS ]
  • C21H38O2Si2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium 2,2,2-trifluoroethanolate In 2,2,2-trifluoroethanol at 20℃; for 0.5h; Inert atmosphere; 4.2.1. General procedure for (4+3)-cycloaddition. Synthesis of 16. General procedure: To a solution of 2-chloro-3,4-bis((trimethylsilyl)methyl)cyclopentanone (100mg, 0.344 mmol) and furan derivative (0.687mmol, 2 equiv) in 2,2,2-trifluoroethanol (1.5mL) was added a 1M sodium 2,2,2-trifluoroethoxide solution (0.52mmol, 1.5equiv) at room temperature and stirred for 0.5 h. The solution was then filtered through a very short pad of alumina (Al2O3) and concentrated under reduced pressure. The crude product was weighed and purified by column chromatography (alumina, 10% EtOAc/hexanes).
  • 68
  • [ 4466-24-4 ]
  • [ 49619-82-1 ]
  • [ 1449481-30-4 ]
YieldReaction ConditionsOperation in experiment
60% With C31H33ClP2Pd; potassium acetate; In N,N-dimethyl acetamide; at 150℃; for 16h;Inert atmosphere; General procedure: The reaction of the <strong>[49619-82-1]3-bromochromen-4-one</strong> (0.225 g, 1 mmol), heteroarene (2 mmol) and KOAc (0.196 g, 2 mmol) at 150 C during 16 h in DMAc (4 mL) with PdCl(C3H5)(dppb) (12.2 mg, 0.02 mmol), under argon affords the coupling product after evaporation of the solvent and purification on silica gel. 3-(2-Ethyl-4-methylthiazol-5-yl)-chromen-4-one (1)
  • 69
  • [ 4466-24-4 ]
  • [ 111-65-9 ]
  • [ 629-82-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: palladium 10% on activated carbon; hydrogen / 16 h / 40 °C / 30003 Torr / Sealed tube 2: palladium 10% on activated carbon; hydrogen; hafnium tetrakis(trifluoromethanesulfonate) / neat (no solvent) / 18 h / 180 °C / 30003 Torr / Sealed tube; Inert atmosphere; Green chemistry 3: palladium 10% on activated carbon; hydrogen; hafnium tetrakis(trifluoromethanesulfonate) / neat (no solvent) / 6 h / 180 °C / 30003 Torr / Sealed tube; Inert atmosphere; Green chemistry
Multi-step reaction with 3 steps 1: palladium 10% on activated carbon; hydrogen / 16 h / 40 °C / 30003 Torr / Sealed tube 2: palladium 10% on activated carbon; hydrogen; hafnium tetrakis(trifluoromethanesulfonate) / neat (no solvent) / 3 h / 180 °C / 30003 Torr / Sealed tube; Inert atmosphere; Green chemistry 3: palladium 10% on activated carbon; hydrogen; hafnium tetrakis(trifluoromethanesulfonate) / neat (no solvent) / 6 h / 180 °C / 30003 Torr / Sealed tube; Inert atmosphere; Green chemistry
  • 70
  • [ 4466-24-4 ]
  • [ 629-82-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: palladium 10% on activated carbon; hydrogen / 16 h / 40 °C / 30003 Torr / Sealed tube 2: palladium 10% on activated carbon; hydrogen; hafnium tetrakis(trifluoromethanesulfonate) / neat (no solvent) / 3 h / 180 °C / 30003 Torr / Sealed tube; Inert atmosphere; Green chemistry
  • 71
  • [ 4466-24-4 ]
  • [ 106-38-7 ]
  • [ 925459-29-6 ]
YieldReaction ConditionsOperation in experiment
99% With potassium acetate; dibromo[1-{2-(4-hydroxyphenyl)ethyl}-3-(2,4,6-trimethylbenzyl) benzimidazole-2-ylidene]-3-chloropyridinepalladium(II) In N,N-dimethyl acetamide at 130℃; Inert atmosphere; Schlenk technique; 2.2. General procedure for Direct Arylation Reactions of Furan and Thiophene with Aryl Halides General procedure: The 2-n-butylfuran and 2-n-butylthiophene (1.5 mmol), the aryl halides (4-bromoacetophenone, 4-bromoanisole and 4- bromotoluene) (1 mmol), KOAc (1 mmol) and PEPPSI type Pd(II)NHC complexes (0.3 mol%) were dissolved in N,N - dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon gas as described in the literature [ 58 , 59 ]. The mix- ture was stirred at 130 °C for 2h. Then, the mixture was filtered through a short pad of celite, the solvents were evaporated under vacuum and the residue was dried in a vacuum. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
87% With bis[1-(1-methyl-2-dimethylaminoethyl)-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.3. General procedure for the direct C5 arylations General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pdcomplexes 2a-d (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a Schlenk tube equipped with a magnetic stirringbar. The Schlenk tube was purged several times with argon andwas placed in a preheated oil bath at 130 C. The reactants werestirred for 1 h with aryl bromides. The solvent was removed byheating the reaction vessel under vacuum. The products wereeluted by using an appropriate ratio of diethyl ether/pentane(1:3). The reaction mixture was purified by flash chromatographyon silica gel. The purity of compounds was checked by GC andNMR. Conversions were based on aryl bromides.
78% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
76% With bis[1,3-di(2,4,6-trimethoxybenzyl)perhydrobenzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction; General procedure for direct C5 arylations General procedure: The required heteroaryl derivative (2 mmol), aryl halide(1 mmol), Pd complex 3a-c (0.005 mmol), KOAc(1 mmol) and DMAc (2 mL) were placed in a Schlenk tube equipped with a magnetic stirring bar. The Schlenk tubewas purged several times with argon and then placed in apreheated oil bath at 130 C, and the reaction mixture was stirred for 1 h. The mixture was analyzed by gas chromatographyto determine the conversion of the aryl bromide and the yield of product. The solvent was removed byheating the reaction vessel under vacuum, and the residuewas charged directly onto a silica gel column. The productswere eluted using diethyl ether/pentane (1:3).
67% With palladium 10% on activated carbon; potassium acetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
58% With dibromo[1-(cyclobutylmethyl)-3-(methoxyethyl)benzimidazole-2-ylidene]pyridine palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.5. General procedure for the arylation reaction General procedure: KOAc (1.0 mmol), aryl-bromide derivatives (1.0 mmol), heteroaryl derivatives (2-nbutylthiazole,2-n-butylthiophene and 2-n-butylfuran) (2.0 mmol) and Pd-NHC-PEPPSIcomplexes 2a-e (0.01 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL)in a small Schlenk tube under argon as described in literature [49]. The reaction mixturewas stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, andthe solvent was removed under vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluentto afford the pure product. The purity of the compounds was checked by gaschromatography (GC) and gas chromatography-mass spectrometry (GC-MS).Conversions were calculated by taking into account the conversion of aryl bromidesto products.
With bis[1-phenyl-3-(1,4-benzodioxano-2-methyl)benzimidazol-2-ylidene]dibromopalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 11 2-n-Butyl-5-(4-methoxyphenyl)furan (11) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
With bis[1-phenyl-3-(3,4,5-trimethoxybenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction;
With 1-naphthalenomethyl-3-benzylbenzimidazol-2-ylidene-N-(3-chloropyridine)dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction; General method for direct arylation General procedure: Heteroaryl derivative (2-n-butylfuran, 2-n-butylthiophene and2-n-propylthiazole) (2 mmol), aryl bromide (p-bromoacetophenone,p-bromoanisole, p-bromotoluene and bromobenzene)(1 mmol), PEPPSI Pd-NHC complexes 2a-f (0.003 mmol), KOAc(1 mmol) and N,N-dimethylacetamide (DMAc) (2 mL) were addedto a small Schlenk tube equipped with a magnetic stirring bar asdescribed in the literature [20-22]. The Schlenk tube was heatedin an oil bath at 130 C for 1 h. When the reaction was completed,the solvent in the reaction media was removed by heating thereaction vessel under vacuum. Then, the pentane and diethylether mixture (3:1) was added to the reaction ambient. As aresult of this process, the obtained product was purified by usingflash chromatography on silica gel. The purity of the compoundwas checked by GC and NMR. Conversions were based on arylbromides.
With bis[1-benzyl-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; 2.7 General Method forDirect Arylation ofFuranandThiophene withAryl Bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone,4-bromoanisole and 4-bromo toluene) (1mmol) and heteroarylderivatives (2-n-butylfuran and 2-n-butylthiophene)(2 mmol), KOAc (1 mmol) and bis-(NHC)Pd(II) complexes1a-f (0.003mmol) were dissolved in N,N-dimethylacetamide(DMAc) (2mL) in a small Schlenk tube underargon as described in the literature [46]. The reaction mixturewas stirred in an oil bath at 130 °C for 1h then wascooled to room temperature and the solvent was removedunder vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by usingdiethyl ether/n-hexane (1:5) as eluent to afford the pureproduct. The purity of the compounds was checked bygas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated bytaking into account the conversion of aryl bromides toproducts.
With bis[1-(2-ethoxyethyl)-3-(4-vinylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; General method for direct arylation of furan and thiophene with aryl bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1mmol) and heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), KOAc (1 mmol) and bis(NHC)-Pd(II) complexes 1a-i (0.003mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2mL) in a small Schlenk tube under argon as described in the literature [22]. The reaction mixture was stirred in an oil bath at 130°C for 1h. Then was cooled to room temperature and the solvent was removed under vacuum. The obtained residue was purified by column chromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
With C44H46Br2N6O6Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; Procedure for arylation of furan, thiophene and thiazole General procedure: The heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), the aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1 mmol), KOAc (1 mmol) and bis-(NHC)PdX2 complexes 1a-i (0.003 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon as described in the literature [31]. The mixture was stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, and the solvent was removed under vacuum. The residue was purified by column chromatography (silica gel 60-120 mesh) using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purities of the compounds were checked by GC and GC-MS. Conversions were calculated based on the aryl bromide.
With C46H40Cl2N4O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique;

Reference: [1]Çağlılar, Tuba; Aktaş, Aydın; Aygün, Muhittin; Behçet, Ayten; Celepci, Duygu Barut; Gök, Yetkin [Journal of Molecular Structure, 2021, vol. 1246]
[2]Yiğit, Murat; Yiğit, Beyhan; Gök, Yetkin [Inorganica Chimica Acta, 2016, vol. 453, p. 23 - 28]
[3]Kaloğlu, Murat; Özdemir, İsmail [Applied Organometallic Chemistry, 2018, vol. 32, # 7]
[4]Yiğit, Beyhan; Yiğit, Murat; Dağdeviren, Zeynep; Özdemir, İsmail [Transition Metal Chemistry, 2016, vol. 41, # 7, p. 751 - 757]
[5]Mao, Shuxin; Shi, Xinzhe; Soulé, Jean-François; Doucet, Henri [Advanced Synthesis and Catalysis, 2018, vol. 360, # 17, p. 3306 - 3317]
[6]Şahin, Neslihan; Serdaroğlu, Goncagül; Düşünceli, Serpil Demir; Tahir, Muhammad Navaz; Arıcı, Cengiz; Özdemir, İsmail [Journal of Coordination Chemistry, 2019, vol. 72, # 19-21, p. 3258 - 3284]
[7]Akkoç, Senem; Gök, Yetkin; Akkurt, Mehmet; Tahir, Muhammad Nawaz [Inorganica Chimica Acta, 2014, vol. 413, p. 221 - 230]
[8]Akkoc, Senem; Gök, Yetkin [Applied Organometallic Chemistry, 2014, vol. 28, # 12, p. 854 - 860]
[9]Akkoç, Senem; Gök, Yetkin [Inorganica Chimica Acta, 2015, vol. 429, p. 34 - 38]
[10]Sarı, Yakup; Aktaş, Aydın; Barut Celepci, Duygu; Gök, Yetkin; Aygün, Muhittin [Catalysis Letters, 2017, vol. 147, # 9, p. 2340 - 2351]
[11]Gök, Yetkin; Aktaş, Aydın; Erdoğan, Hülya; Sarı, Yakup [Inorganica Chimica Acta, 2018, vol. 471, p. 735 - 740]
[12]Erdoğan, Hülya; Aktaş, Aydın; Gök, Yetkin; Sarı, Yakup [Transition Metal Chemistry, 2018, vol. 43, # 1, p. 31 - 37]
[13]Gök, Yetkin; Aktaş, Aydın; Sarı, Yakup; Erdoğan, Hülya [Journal of the Iranian Chemical Society, 2019, vol. 16, # 2, p. 423 - 433]
  • 72
  • [ 4466-24-4 ]
  • [ 108-86-1 ]
  • [ 80866-26-8 ]
YieldReaction ConditionsOperation in experiment
99% With dibromo[1-(cyclobutylmethyl)-3-(methoxyethyl)benzimidazole-2-ylidene]pyridine palladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.5. General procedure for the arylation reaction General procedure: KOAc (1.0 mmol), aryl-bromide derivatives (1.0 mmol), heteroaryl derivatives (2-nbutylthiazole,2-n-butylthiophene and 2-n-butylfuran) (2.0 mmol) and Pd-NHC-PEPPSIcomplexes 2a-e (0.01 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL)in a small Schlenk tube under argon as described in literature [49]. The reaction mixturewas stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, andthe solvent was removed under vacuum. The obtained residue was purified by columnchromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluentto afford the pure product. The purity of the compounds was checked by gaschromatography (GC) and gas chromatography-mass spectrometry (GC-MS).Conversions were calculated by taking into account the conversion of aryl bromidesto products.
98% With N,N-dimethyl acetamide; dichloro[1,3-bis(N-phthalimidomethyl)benzimidazol-2-ylidene](3-chloropyridine) palladium(II); potassium acetate at 110℃; for 21h; Inert atmosphere; Schlenk technique; General procedure for the arylation reaction General procedure: All catalytic reactions were carried out under an air atmosphere. The purchased reagents were used without further purifications for C-C bond forming reactions. In a typical reaction, 2-n-butylfuran or 2-n-butylthiophene (2 mmol), aryl bromides (1 mmol), KOAc (1 mmol), PEPPSI Pd-NHC (1 mol %) and N,N-dimethylacetamide (DMAc, 2 mL) were added to a dry 25 mL Schlenk tube. The mixture was then stirred for different times at different temperatures. After the reaction was finished, the solvent in the medium was removed completely by vacuum and the remaining solid in the Schlenk tube was dissolved in hexane/diethyl ether (5:1), before it was purified over silica gel. The chemical characterisations of the products were made by GC or GC-MS. The yields were calculated according to aryl bromides as internal references. The results are given in Table 1.
86% With potassium acetate; palladium diacetate; 2,3,5,6-tetrakis(N-4-tert-butylbenzylbenzimidazoliummethyl)benzene tetrabromide In N,N-dimethyl acetamide for 1h; Inert atmosphere; Schlenk technique; Heating; Green chemistry; General procedure for direct arylation of heteroaromatics General procedure: Under argon atmosphere, heteroaryl derivative (2-n-propylthiazole, 2-n-butylthiophene, 2-n-butylfuran and 4,5-dimethylthiazole) (2 mmol), 4-bromobenzene or 4-bromoacetophenone (1 mmol), KOAc (2 mmol), Pd(OAc)2 ( 0.005 mmol), 1a-1f (0.00125 mmol), DMAc (3 mL) were added into Schlenk tube. The mixture was stirred strongly at 130 oC for 1h. The solvent was removed under a vacuum. The product was eluted using a pentane-diethyl ether mixture (3:1). The reaction mixture was purified by flash chromatography on silica gel. GC yields were calculated relative to aryl bromide.
83% With bis[1-(1-methyl-2-dimethylaminoethyl)-3-(2,3,4,5,6-pentamethylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 2.3. General procedure for the direct C5 arylations General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pdcomplexes 2a-d (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a Schlenk tube equipped with a magnetic stirringbar. The Schlenk tube was purged several times with argon andwas placed in a preheated oil bath at 130 C. The reactants werestirred for 1 h with aryl bromides. The solvent was removed byheating the reaction vessel under vacuum. The products wereeluted by using an appropriate ratio of diethyl ether/pentane(1:3). The reaction mixture was purified by flash chromatographyon silica gel. The purity of compounds was checked by GC andNMR. Conversions were based on aryl bromides.
78% With bis[1,3-di(2,4,6-trimethoxybenzyl)perhydrobenzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction; General procedure for direct C5 arylations General procedure: The required heteroaryl derivative (2 mmol), aryl halide(1 mmol), Pd complex 3a-c (0.005 mmol), KOAc(1 mmol) and DMAc (2 mL) were placed in a Schlenk tube equipped with a magnetic stirring bar. The Schlenk tubewas purged several times with argon and then placed in apreheated oil bath at 130 C, and the reaction mixture was stirred for 1 h. The mixture was analyzed by gas chromatographyto determine the conversion of the aryl bromide and the yield of product. The solvent was removed byheating the reaction vessel under vacuum, and the residuewas charged directly onto a silica gel column. The productswere eluted using diethyl ether/pentane (1:3).
77% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
With bis[1-phenyl-3-(2-morpholinoethyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; 12 2-n-Butyl-5-(4-methylphenyl)furan (12) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
With bis[1-(2-morpholinoethyl)-3-(2-methylbenzyl)benzimidazol-2-ylidene]dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction;
With 1-phenyl-3-(2,3,5,6-tetramethylbenzyl)benzimidazol-2-ylidene-N-(3-chloropyridine)dichloropalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; regioselective reaction; General method for direct arylation General procedure: Heteroaryl derivative (2-n-butylfuran, 2-n-butylthiophene and2-n-propylthiazole) (2 mmol), aryl bromide (p-bromoacetophenone,p-bromoanisole, p-bromotoluene and bromobenzene)(1 mmol), PEPPSI Pd-NHC complexes 2a-f (0.003 mmol), KOAc(1 mmol) and N,N-dimethylacetamide (DMAc) (2 mL) were addedto a small Schlenk tube equipped with a magnetic stirring bar asdescribed in the literature [20-22]. The Schlenk tube was heatedin an oil bath at 130 C for 1 h. When the reaction was completed,the solvent in the reaction media was removed by heating thereaction vessel under vacuum. Then, the pentane and diethylether mixture (3:1) was added to the reaction ambient. As aresult of this process, the obtained product was purified by usingflash chromatography on silica gel. The purity of the compoundwas checked by GC and NMR. Conversions were based on arylbromides.
With bis[1-ethyl-3-(4-vinylbenzyl)benzimidazol-2-ylidene]dichloropalladium; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Schlenk technique; Inert atmosphere; General method for direct arylation of furan and thiophene with aryl bromides General procedure: The aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1mmol) and heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), KOAc (1 mmol) and bis(NHC)-Pd(II) complexes 1a-i (0.003mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2mL) in a small Schlenk tube under argon as described in the literature [22]. The reaction mixture was stirred in an oil bath at 130°C for 1h. Then was cooled to room temperature and the solvent was removed under vacuum. The obtained residue was purified by column chromatography (silica gel 60-120 mesh) by using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purity of the compounds was checked by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Conversions were calculated by taking into account the conversion of aryl bromides to products.
With C42H42Br2N6O6Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique; Procedure for arylation of furan, thiophene and thiazole General procedure: The heteroaryl derivatives (2-n-butylfuran, 2-n-butylthiophene and 2-isopropylthiazole) (2 mmol), the aryl bromide derivatives (4-bromo acetophenone, 4-bromoanisole, 4-bromotoluene and 4-bromobenzene) (1 mmol), KOAc (1 mmol) and bis-(NHC)PdX2 complexes 1a-i (0.003 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (2 mL) in a small Schlenk tube under argon as described in the literature [31]. The mixture was stirred in an oil bath at 130 °C for 1 h, then cooled to room temperature, and the solvent was removed under vacuum. The residue was purified by column chromatography (silica gel 60-120 mesh) using diethyl ether/n-hexane (1:5) as eluent to afford the pure product. The purities of the compounds were checked by GC and GC-MS. Conversions were calculated based on the aryl bromide.
With C34H32Br2N4O4Pd; potassium acetate In N,N-dimethyl acetamide at 130℃; for 1h; Inert atmosphere; Schlenk technique;

  • 73
  • [ 4466-24-4 ]
  • [ 106-43-4 ]
  • [ 925459-29-6 ]
YieldReaction ConditionsOperation in experiment
72% With dibromo‐bis[1,3‐di(4‐phenoxybutyl)benzimidazol‐2‐ylidene]palladium(II); potassium acetate In N,N-dimethyl acetamide at 120℃; for 20h; Inert atmosphere; Schlenk technique;
70% With tetrabutylammomium bromide; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 120℃; for 20h; Inert atmosphere;
With bis[1-phenyl-3-(1,4-benzodioxano-2-methyl)benzimidazol-2-ylidene]dibromopalladium(II); potassium acetate In N,N-dimethyl acetamide at 130℃; for 20h; Schlenk technique; Inert atmosphere; 16 2-n-Butyl-5-acetophenylfuran (16) General procedure: The heteroaryl derivative (2 mmol), aryl halide (1 mmol), Pd complexes 1a-e (0.005 mmol), KOAc (1 mmol) and DMAc (2 mL)were added into a schlenk tube equipped with a magnetic stirring bar. The Schlenk tube was purged several times with argon and was placed in a pre heated oil bath at 130°C. The reactants were stirred for 1 h (with aryl bromides) and for 20h (with aryl chlorides). The solvent was removed by heating the reaction vessel under vacuum. The products were eluted by using an appropriate ratio of diethyl ether/pentane (1:3). The reaction mixture was purified by flash chromatography on silica gel. The purity of compounds was checked by GC and NMR. Yields were based onaryl halides (aryl bromide and aryl chloride).
  • 74
  • [ 4466-24-4 ]
  • [ 3034-31-9 ]
  • [ 1522465-02-6 ]
  • 75
  • [ 110-00-9 ]
  • [ 693-04-9 ]
  • [ 4466-24-4 ]
YieldReaction ConditionsOperation in experiment
37% With C31H38ClN3NiO2(1-)*Li(1+) In diethyl ether; ethylene dibromide at 25℃; for 1h; Inert atmosphere;
33% With C31H37ClFeN3O2 In diethyl ether; ethylene dibromide at 25℃; for 1h; Inert atmosphere; 2.4. Cross coupling of oxygen containing heterocyclics withGrignard reagents General procedure: Cross coupling reactions of Grignard reagents with other hete-rocyclics such as furan and dioxane were performed according tothe following general method.An aliquot of Catalyst 1 (0.5 mg, 0.87 mol) in diethyl ether wasadded using a gas-tight syringe to a 5 mL round bottom flask purgedwith argon. To this solution, phenylmagnesium chloride in ether(0.92 mmol) followed by dibromoethane (90 L, 1.04 mol) wereadded and allowed to stir at room temperature. Samples for anal-ysis were collected at the appointed time intervals over a period of60 min. Excess Grignard reagent was destroyed using methanol andthe reaction products were quantitated by GC-MS using an internalstandard 2-methyltetrahydrofuran. Product yields were reportedin turnover number (TON: moles of product formed per mole of cat-alyst used) and turnover frequency (TOF: moles of product formedper mole of catalyst in unit time). For large scale synthesis, thecompound was worked up and isolated as mentioned above.
  • 76
  • [ 4466-24-4 ]
  • [ 98-09-9 ]
  • [ 80866-26-8 ]
YieldReaction ConditionsOperation in experiment
41% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 72h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-phenylfuran (1) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
41% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 72h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans. 2-Butyl-5-phenylfuran (1)142-Butylfuran (0.124 g, 1 mmol) and benzenesulfonyl chloride(0.264 g, 1.5 mmol) afforded 1 (0.082 g, 41%) as a colorless oil.1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 8.0 Hz, 2 H), 7.27 (t,J = 8.0 Hz, 2 H), 7.13 (t, J = 8.0 Hz, 1 H), 6.46 (d, J = 3.2 Hz, 1 H),5.98 (d, J = 3.2 Hz, 1 H), 2.61 (t, J = 7.3 Hz, 2 H), 1.59 (quint, J =7.3 Hz, 2 H), 1.33 (sext, J = 7.3 Hz, 2 H), 0.87 (t, J = 7.3 Hz, 3 H).
  • 77
  • [ 4466-24-4 ]
  • [ 98-74-8 ]
  • [ 925459-27-4 ]
YieldReaction ConditionsOperation in experiment
88% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(4-nitrophenyl)furan (2) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
88% With dichloro bis(acetonitrile) palladium(II); lithium carbonate at 140℃; for 15h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction;
88% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 78
  • [ 4466-24-4 ]
  • [ 49584-26-1 ]
  • [ 925459-26-3 ]
YieldReaction ConditionsOperation in experiment
91% With dichloro bis(acetonitrile) palladium(II); lithium carbonate at 140℃; for 15h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction;
89% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(4-cyanophenyl)furan (3) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
89% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 79
  • [ 4466-24-4 ]
  • [ 2991-42-6 ]
  • [ 1042318-49-9 ]
YieldReaction ConditionsOperation in experiment
90% With dichloro bis(acetonitrile) palladium(II); lithium carbonate at 140℃; for 15h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction;
79% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-[4-(trifluoromethyl)phenyl]furan (4) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
79% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 80
  • [ 4466-24-4 ]
  • [ 98-60-2 ]
  • 2-n-butyl-5-(4-chlorophenyl)furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With dichloro bis(acetonitrile) palladium(II); lithium carbonate at 140℃; for 15h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction;
50% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(4-chlorophenyl)furan (5) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
50% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 81
  • [ 4466-24-4 ]
  • [ 98-61-3 ]
  • 2-n-butyl-5-(4-iodophenyl)furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
70% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 82
  • [ 4466-24-4 ]
  • [ 349-88-2 ]
  • [ 925459-28-5 ]
YieldReaction ConditionsOperation in experiment
32% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(4-fluorophenyl)furan (7) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
32% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 83
  • [ 4466-24-4 ]
  • [ 777-44-6 ]
  • 2-n-butyl-5-(3-(trifluoromethyl)phenyl)furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-[3-(trifluoromethyl)phenyl]furan (9) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
62% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
48% With dichloro bis(acetonitrile) palladium(II); lithium carbonate at 140℃; for 15h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction;
  • 84
  • [ 4466-24-4 ]
  • [ 2888-06-4 ]
  • 2-n-butyl-5-(3-chlorophenyl)furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
73% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 85
  • [ 4466-24-4 ]
  • [ 39234-86-1 ]
  • 2-[3,5-bis(trifluoromethyl)phenyl]-5-n-butylfuran [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
75% With dichloro bis(acetonitrile) palladium(II); lithium carbonate; In 1,4-dioxane; at 140℃; for 40h;Schlenk technique; Inert atmosphere; General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 86
  • [ 4466-24-4 ]
  • [ 69360-26-5 ]
  • [ 1042318-52-4 ]
YieldReaction ConditionsOperation in experiment
83% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(2-cyanophenyl)furan (12) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
83% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
  • 87
  • [ 4466-24-4 ]
  • [ 2905-21-7 ]
  • 2-n-butyl-5-(2-fluorophenyl)furan [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; 2-Butyl-5-(2-fluorophenyl)furan (13) General procedure: To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) were added successively. The mixture was evacuated by vacuum-argon cycles (5 ×) and stirred at 140 °C (oil bath temperature) for 20-72 h (see tables and schemes). After cooling the reaction at r.t. and concentration, the crude mixture was purified by column chromatography (silica gel) to afford the C5-arylated furans.
89% With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 40h; Schlenk technique; Inert atmosphere; regioselective reaction; C5-Arylated Furans; General Procedure General procedure: C5-Arylated Furans; General Procedure To a 25-mL oven-dried Schlenk tube, arenesulfonyl chloride (1.5-2 mmol), furan derivative (1 mmol), Li2CO3 (0.222 g, 3 mmol), 1,4-dioxane (2 mL) and PdCl2(MeCN)2 (12.9 mg, 0.05 mmol) wereadded successively. The mixture was evacuated by vacuum-argoncycles (5 ) and stirred at 140 °C (oil bath temperature) for 20-72 h(see tables and schemes). After cooling the reaction at r.t. and con-centration, the crude mixture was purified by column chromatogra-phy (silica gel) to afford the C5-arylated furans.
Recommend Products
Same Skeleton Products
Historical Records

Related Parent Nucleus of
[ 4466-24-4 ]

Furans

Chemical Structure| 3777-69-3

[ 3777-69-3 ]

2-Pentylfuran

Similarity: 1.00

Chemical Structure| 83469-85-6

[ 83469-85-6 ]

2-Decylfuran

Similarity: 1.00

Chemical Structure| 57640-17-2

[ 57640-17-2 ]

1,4-Di(furan-2-yl)butane

Similarity: 1.00

Chemical Structure| 72636-53-4

[ 72636-53-4 ]

2,5-Dibutylfuran

Similarity: 0.97

Chemical Structure| 89834-67-3

[ 89834-67-3 ]

2,5-Dipentylfuran

Similarity: 0.97