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[ CAS No. 14918-21-9 ] {[proInfo.proName]}

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Cat. No.: {[proInfo.prAm]}
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3d Animation Molecule Structure of 14918-21-9
Chemical Structure| 14918-21-9
Chemical Structure| 14918-21-9
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Product Details of [ 14918-21-9 ]

CAS No. :14918-21-9 MDL No. :MFCD00001978
Formula : C6H7N Boiling Point : -
Linear Structure Formula :NC(CH2)3CCH InChI Key :JZYKFLLRVPPISG-UHFFFAOYSA-N
M.W : 93.13 Pubchem ID :139852
Synonyms :

Calculated chemistry of [ 14918-21-9 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 7
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.5
Num. rotatable bonds : 2
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 28.87
TPSA : 23.79 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.26 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.63
Log Po/w (XLOGP3) : 0.85
Log Po/w (WLOGP) : 1.39
Log Po/w (MLOGP) : 1.28
Log Po/w (SILICOS-IT) : 1.23
Consensus Log Po/w : 1.28

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -0.82
Solubility : 14.1 mg/ml ; 0.151 mol/l
Class : Very soluble
Log S (Ali) : -0.93
Solubility : 10.9 mg/ml ; 0.117 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -1.17
Solubility : 6.28 mg/ml ; 0.0675 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.64

Safety of [ 14918-21-9 ]

Signal Word:Danger Class:3
Precautionary Statements:P210-P233-P240-P241-P242-P243-P260-P261-P264-P270-P271-P280-P301+P312-P302+P352-P303+P361+P353-P304-P304+P340-P305+P351+P338-P312-P321-P322-P330-P332+P313-P337+P313-P340-P362-P363-P370+P378-P403-P403+P233-P403+P235-P405-P501 UN#:1993
Hazard Statements:H225-H302-H312-H315-H319-H332-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 14918-21-9 ]

* 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 [ 14918-21-9 ]

[ 14918-21-9 ] Synthesis Path-Downstream   1~100

  • 3
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • [ 108-98-5 ]
  • (Z)-7-Oxo-5-phenylsulfanyl-hept-5-enenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With carbonylhydridetris(triphenylphosphine)rhodium(I) In acetonitrile at 120℃; for 5h;
  • 4
  • [ 14918-21-9 ]
  • [ 178988-68-6 ]
  • ((Z)-5-Cyano-2-phenylselanyl-pent-1-enyl)-phosphonic acid diphenyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 67℃; for 20h;
  • 5
  • [ 14918-21-9 ]
  • [ 56752-35-3 ]
  • 6-[9-(5-Cyano-pent-1-ynyl)-perylen-3-yl]-hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
With piperidine In tetrahydrofuran at 80℃; for 14h; Yield given;
  • 6
  • [ 29768-03-4 ]
  • [ 14918-21-9 ]
  • (3-Pyridin-2-yl-6,7-dihydro-5H-[1]pyrindin-2-yl)-methanol [ No CAS ]
  • (2-Pyridin-2-yl-6,7-dihydro-5H-[1]pyrindin-3-yl)-methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 15% 2: 4% With dicarbonylcyclopentadienylcobalt In toluene for 7h; Heating; Irradiation;
  • 7
  • [ 1569-69-3 ]
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • 5-Cyano-2-methylene-pentanethioic acid S-cyclohexyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With tetrakis(triphenylphosphine)platinum In acetonitrile at 120℃;
82% In acetonitrile at 120℃;
  • 8
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • [ 108-98-5 ]
  • 5-Cyano-2-methylene-pentanethioic acid S-phenyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tetrakis(triphenylphosphine)platinum In acetonitrile at 120℃;
75% In acetonitrile at 120℃;
  • 9
  • [ 14918-21-9 ]
  • [ 3031-68-3 ]
  • (3'-Hydroxymethyl-6,7,6',7'-tetrahydro-5H,5'H-[2,2']bi[[1]pyrindinyl]-3-yl)-methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
9% With cyclopentadienyl-biscarbonyl-cobalt(I) In toluene for 1h; Heating; Irradiation;
9% In toluene for 1h; Irradiation; heating;
  • 10
  • [ 14918-21-9 ]
  • [ 2177-34-6 ]
  • (E)-5-Chloro-9-cyclohexyl-9-oxo-non-5-enenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride; tin(IV) chloride; tetramethlyammonium chloride In N,N-dimethyl-formamide at 60℃;
  • 11
  • [ 14918-21-9 ]
  • [ 78-94-4 ]
  • (E)-5-Chloro-9-oxo-dec-5-enenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride; tin(IV) chloride; ammonium chloride In water; N,N-dimethyl-formamide at 60℃;
  • 12
  • [ 14918-21-9 ]
  • [ 111-81-9 ]
  • (9E,12E)-16-Cyano-hexadeca-9,12-dienoic acid methyl ester [ No CAS ]
  • (E)-15-Cyano-12-methylene-pentadec-9-enoic acid methyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
With cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate; camphor-10-sulfonic acid In acetone at 50℃;
With cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate In N,N-dimethyl-formamide at 20℃;
With acetone In water at 20℃; for 2h; Title compound not separated from byproducts.;
With acetone In water Heating; Title compound not separated from byproducts.;

  • 13
  • [ 14918-21-9 ]
  • [ 3523-02-2 ]
YieldReaction ConditionsOperation in experiment
88% With water In isopropyl alcohol at 130℃; for 12h;
78% With water In acetone at 120℃; for 96h;
98 % Spectr. With water In acetone at 69 - 72℃; for 40h;
97.8 % Spectr. With [CpRu(6-Ph2P-Py-2-yl)(MeCN)][PF6(1-)]; water In acetone at 70℃; for 96h;
With (2-(diphenylphosphino)-6-(2,4,6-triisopropylphenyl)pyridine); chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In water; acetone at 160℃; for 0.25h; Microwave irradiation; Inert atmosphere;

  • 14
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • [ 108-98-5 ]
  • [ 147766-06-1 ]
  • 5-Cyano-2-methylene-pentanethioic acid S-phenyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 85% 2: 13% With toluene-4-sulfonic acid In tetrahydrofuran at 110℃; for 6h;
  • 15
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • [ 106-45-6 ]
  • [ 147766-06-1 ]
  • 2-(3-cyano-propyl)-thioacrylic acid <i>S</i>-<i>p</i>-tolyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 84% 2: 10% With toluene-4-sulfonic acid In tetrahydrofuran at 110℃; for 6h;
  • 16
  • [ 16352-18-4 ]
  • [ 14918-21-9 ]
  • (E)-6-(4,4,5,5-Tetramethyl-2-oxo-2λ5-[1,3,2]dioxaphospholan-2-yl)-hex-5-enenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With tris(triphenylphosphine)rhodium(I) chloride In acetone at 25℃; for 20h;
  • 17
  • [ 14918-21-9 ]
  • [ 105496-31-9 ]
  • [ 452282-75-6 ]
  • 4-acetoxy-3-methoxy-5-(5-cyano-1-pentynyl)-N-(2-hydroxyethyl)-benzenepropanamide [ No CAS ]
  • 18
  • [ 14918-21-9 ]
  • [ 3186-52-5 ]
  • methyl (Z)-6-cyano-3-phenylthio-2-hexenoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With palladium(0)bis(tricyclohexylphosphine) In octane; toluene at 110℃; for 20h;
  • 19
  • [ 14918-21-9 ]
  • [ 78-94-4 ]
  • [ 59250-81-6 ]
YieldReaction ConditionsOperation in experiment
63% With tris(o-methoxyphenyl)phosphine In benzene for 24h; Heating;
62% With pyrrolidine In benzene at 60℃; for 12h;
  • 20
  • [ 14918-21-9 ]
  • [ 33775-94-9 ]
  • [ 415680-01-2 ]
YieldReaction ConditionsOperation in experiment
99% With copper(l) iodide; triethylamine at 20℃; for 5h;
92% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃;
89% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃;
  • 21
  • [ 14918-21-9 ]
  • [ 768-03-6 ]
  • 5-bromo-9-oxo-9-phenyl-non-5-enenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate; stannic bromide; lithium bromide In acetone at 60℃; for 2h;
  • 22
  • [ 14918-21-9 ]
  • Dibenzyl-((E)-pent-1-enyl)-amine [ No CAS ]
  • 7-(dibenzylamino)-5-undecynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With copper(I) bromide In toluene at 60℃; for 5h;
82% With copper(I) bromide In decane; toluene at 60℃; for 5h;
  • 23
  • [ 14918-21-9 ]
  • [ 6630-33-7 ]
  • [ 1055320-23-4 ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: ortho-bromobenzaldehyde With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 25℃; for 0.25h; Inert atmosphere; Stage #2: 5-cyano-1-pentyne at 60℃; for 12h; Inert atmosphere;
78% With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In tetrahydrofuran at 0 - 45℃; Inert atmosphere; Schlenk technique;
64% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine
With triethylamine at 55℃;
Stage #1: 5-cyano-1-pentyne; ortho-bromobenzaldehyde With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In N,N-dimethyl-formamide at 20℃; Stage #2:

  • 24
  • [ 14918-21-9 ]
  • [ 54353-18-3 ]
  • (4-Cyano-1-methylene-butyl)-phenyl-phosphinic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With Me<SUB>2</SUB>Pd(PPhMe<SUB>2</SUB>)<SUB>2</SUB>; diphenyl-phosphinic acid In toluene at 70℃; for 4.5h;
  • 25
  • [ 14918-21-9 ]
  • [ 10412-98-3 ]
YieldReaction ConditionsOperation in experiment
83% With methyl(triphenylphosphine)gold(I); sulfuric acid In methanol; water at 70℃; for 1h;
83% With water In methanol at 70℃; for 1h; 34 Example 34 Example 34 To a solution in which 0.001 g of methyl(triphenylphosphine)gold (0.002 mmol) was dissolved in 1 ml of methanol, 0.11 g of 5-hexynenitrile (1 mmol) and an aqueous solution in which 0.05 g of concentrated sulfuric acid (0.5 mmol) was dissolved in 0.5 ml of water were added. After stirring at 70° C. for 1 hour, the yield of 5-oxohexanitrile was 83% (catalyst turnover number: 465).
82% With water; silver trifluoromethanesulfonate for 10h; Heating;
76% With morpholine; Au-TiO2; water In 1,4-dioxane at 110℃; for 2h; Microwave irradiation;
92 %Chromat. With silver hexafluoroantimonate; water In methanol at 75℃; for 24h; chemoselective reaction;
83 %Chromat. With methyl(triphenylphosphine)gold(I); sulfuric acid; water In methanol at 70℃; for 1h; Inert atmosphere;

  • 26
  • [ 14918-21-9 ]
  • [ 4873-09-0 ]
  • 1,3-di(3-cyanopropyl)-4-methylbenzene [ No CAS ]
  • 27
  • [ 14918-21-9 ]
  • [ 698-02-2 ]
  • 6-(2-N,N-dimethylaminophenyl)-5-hexynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
40% With copper(l) iodide; triethylamine at 20℃; for 7h;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 60℃; for 0.333333h; Microwave irradiation;
  • 28
  • [ 593-60-2 ]
  • [ 14918-21-9 ]
  • [ 820964-75-8 ]
YieldReaction ConditionsOperation in experiment
70% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In tetrahydrofuran; triethylamine at 20℃; for 6.5h;
70% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃; for 7h; Inert atmosphere;
  • 29
  • [ 14918-21-9 ]
  • [ 544-25-2 ]
  • 4-bicyclo[4.2.1]nona-2,4,7-trien-7-ylbutanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With zinc(II) iodide; zinc In 1,2-dichloro-ethane at 40℃; for 20h;
  • 30
  • [ 14918-21-9 ]
  • [ 696-62-8 ]
  • 6-(4-methoxy-phenyl)-hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With tetrabutylammonium acetate In N,N-dimethyl-formamide at 20℃; for 6h;
70% With tris-(dibenzylideneacetone)dipalladium(0); sodium hydroxide In ethanol; water at 80℃; for 1h; Under air;
59% With copper(l) iodide; bis(benzonitrile)palladium(II) dichloride; triethylamine at 85℃; for 12h; Schlenk technique; Inert atmosphere;
  • 31
  • [ 14918-21-9 ]
  • (E)-N-(2-iodobenzylidene)-2-methylpropan-2-amine [ No CAS ]
  • 4-(isoquinolin-3-yl)butanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With zinc In acetonitrile at 80℃; for 0.333333h;
  • 32
  • [ 14918-21-9 ]
  • [ 431-03-8 ]
  • 7-hydroxy-7-methyl-8-oxonon-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With acetylacetonatodicarbonylrhodium(l); johnphos In tetrahydrofuran at 40℃; for 24h;
98% With johnphos In tetrahydrofuran at 40℃; for 24h;
  • 33
  • [ 14918-21-9 ]
  • [ 629-20-9 ]
  • 4-(bicyclo[4.2.2]deca-2,4,7,9-tetraen-7-yl)butanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With zinc(II) iodide; zinc In 1,2-dichloro-ethane at 40℃; for 20h;
  • 34
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • [ 117044-76-5 ]
  • (Z)-6-Cyano-3-(2,4,5-trichloro-phenylsulfanyl)-hex-2-enoic acid diethylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With tetrabutyl-ammonium chloride; triphenylphosphine In acetonitrile at 120℃; for 3h;
  • 35
  • [ 110-91-8 ]
  • [ 14918-21-9 ]
  • [ 201230-82-2 ]
  • 5-(morpholine-4-carbonyl)-hex-5-enenirtile [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With [bmim][Tf2N]; 1,3-bis-(diphenylphosphino)propane at 110℃; for 22h;
  • 36
  • [ 3437-95-4 ]
  • [ 14918-21-9 ]
  • [ 934423-94-6 ]
YieldReaction ConditionsOperation in experiment
95% With piperidine; copper(l) iodide In tetrahydrofuran at 50℃;
  • 37
  • [ 273208-11-0 ]
  • [ 14918-21-9 ]
  • [ 929205-87-8 ]
YieldReaction ConditionsOperation in experiment
94% With triethylamine; triphenylphosphine In acetonitrile at 80℃; for 24h;
92% Stage #1: N-methyl-2-iodo-4-methyl-benzenesulfonamide With copper(l) iodide; triethylamine; triphenylphosphine In acetonitrile at 25℃; for 0.5h; Stage #2: 5-hexynonitrile In acetonitrile at 80℃; for 10h; Further stages.;
  • 38
  • [ 14918-21-9 ]
  • [ 5296-64-0 ]
  • 8-cyano-5-phenylthio-octa-1,4(Z)-diene [ No CAS ]
  • 2-(3'-cyanopropyl)-1-phenylthio-penta-1(Z),4-diene [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 60℃; for 8h;
  • 39
  • [ 14918-21-9 ]
  • [ 89641-06-5 ]
  • 4-(1-oxo-1,2-dihydro-isoquinolin-3-yl)-butyronitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% Stage #1: 2-iodo benzoyl azide With copper(l) iodide; triethylamine; triphenylphosphine In ethanol at 25℃; for 0.5h; Stage #2: 5-hexynonitrile In ethanol at 80℃; for 12h; Further stages.;
  • 40
  • [ 945858-23-1 ]
  • [ 14918-21-9 ]
  • 4-(5-methoxy-1-oxo-1,2-dihydro-isoquinolin-3-yl)-butyronitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% Stage #1: C8H6IN3O2 With copper(l) iodide; triethylamine; triphenylphosphine In ethanol at 25℃; Stage #2: 5-hexynonitrile In ethanol at 80℃; for 12h; Further stages.;
  • 41
  • [ 14918-21-9 ]
  • [ 22825-21-4 ]
  • 6-(2,2-diphenylcyclopropyl)hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With triethylamine In tetrahydrofuran at 23℃; for 24h;
42% With trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) In 1,2-dichloro-ethane at 20℃; for 4h; Inert atmosphere;
  • 42
  • [ 14918-21-9 ]
  • [ 65051-83-4 ]
  • C16H17N [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With triethylamine In tetrahydrofuran at 23℃; for 24h;
  • 43
  • [ 14918-21-9 ]
  • [ 167558-54-5 ]
  • 6-(1H-indol-2-yl)hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With copper(l) iodide; diisopropylamine In toluene at 100℃; for 24h;
50% With diisopropylamine In toluene at 100℃; for 24h; 5g; A Example 5g: Preparation of 6-(l//-Indol-2-yl)hex-5-ynenitrileA carousel reaction tube (24x 150 mm) was charged with 2-(2,2-dibromovinyl)aniline (139 mg, 0.50 mmol), Pearlman's catalyst (Degussa E4) (10.6 mg, 0.0087 mmol, 2 mol%), PO-OMePh)3 (14.1 mg, 0.040 mmol, 8 mol%), and CuI (3.9 mg, 0.020 mmol, 4 mol%), and was evacuated and purged with argon three times. To this mixture were added toluene (3 mL, degassed), /Pr2NH (180 μL, 1.28 mmol) and 5-hexynenitrile (80 μL, 0.75 mmol), and then heated to 100 0C with stirring for 24 h. The reaction mixture was then cooled to rt and H2O (10 mL) added. The mixture was extracted with EtOAc (2 x 15 mL), and combined extracts were washed with sat. NH4Cl and brine, then dried and solvent was removed in vacuo. The resulting crude material was purified by flash chromatography eluting with 25% EtOAc in hexane to afford the titled compound as a pale brown oil (52.3 mg, 50%). IR (CHCl3) v 3390, 2358, 1995, 1350, 1295 cm"1; 1H- NMR (CDCl3) δ: 8.23 (IH, s), 7.56 (IH, d, J= 7.9 Hz), 7.33-7.07 (3H, m), 6.68 (IH, br s), 2.65 (2H, t, J = 6.7 Hz), 2.56 (2H, t, J = 7.0 Hz), 2.03-1.92 (2H, m); 13C NMR (75 MHz, CDCl3) δ 136.0, 127.8, 123.5, 120.9, 120.6, 119.4, 118.8, 110.9, 108.2, 90.6, 75.2, 24.5, 19.0, 16.5; HRMS (EI) m/z calcd.for: [M]+ 208.1000, m/z found: 208.0996.
  • 44
  • [ 14918-21-9 ]
  • [ 91703-34-3 ]
  • (6-benzofuran-2-yl)hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With copper(l) iodide; diisopropylamine In water; toluene at 100℃; for 12h;
76% With diisopropylamine In water; toluene at 100℃; for 12h; 6g Example 6g: Preparation of (6-Benzofuran-2-yl)hex-5-ynenitrileA carousel reaction tube (24x 150 mm) was charged with 2-(2,2-dibromovinyl)phenol [prepared from salicylaldehyde according to the procedure by Bisseret (Thielges, S.; Meddah, E.; Bisseret, P.; Eustache, J. Tetrahedron Lett. 2004, 907)] (120 mg, 0.43 mmol), Pearlman's catalyst (Degussa E4) (4.6 mg, 0.0043 mmol, 1 mol%), P(^-MeOPh)3 (6.1 mg, 0.017 mmol, 4 mol%), and CuI (1.7 mg, 0.0086 mmol, 2 mol%), and was evacuated and purged with argon three times. To this mixture were added toluene (2 mL, degassed), H2O (1 mL, degassed), /Pr2NH (160 μL, 1.18 mmol) and 5-hexynenitrile (70 μL, 0.65 mmol), and then heated to 100 0C with stirring for 12 h. The reaction mixture was then cooled to rt and H2O (10 mL) added. The mixture was extracted with EtOAc (2 x 15 mL), and combined extracts were washed with sat. NH4Cl and brine, then dried and solvent was removed in vacuo. The resulting crude material was purified by flash chromatography eluting with 15% EtOAc in hexane to afford the titled compound as a colorless oil (68.5 mg, 76%). IR (CHCl3) v 3061, 2945, 2246, 1732, 1568, 1450, 1428, 1351, 1306, 1253, 1199, 1158, 1142, 1109, 1010 cm'1; 1H-NMR (CDCl3) δ: 7.54 (IH, d, J = 7.6 Hz), 7.44 (IH, d, J= 8.2 Hz), 7.37-7.20 (2H, m), 6.87 (IH, s), 2.70 (2H, t, J= 6.9 Hz), 2.58 (2H, t, J= 6.9 Hz), 2.03 (2H, q, J= 6.9 Hz); 13C NMR (75 MHz, DMSO-J6) δ 154.8, 138.6, 127.7, 125.7, 123.4, 121.3, 119.1, 111.3, 111.2, 93.6, 73.3, 24.4, 18.9, 16.5; HRMS (EI) m/z calcd.for: [M]+ 209.0841, m/z found: 209.0839.
  • 45
  • [ 14918-21-9 ]
  • 1,10-biscyanodeca-4,6-diyne [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% With N,N,N,N,-tetramethylethylenediamine In dichloromethane at 130℃; for 0.333333h; Flow reactor; chemoselective reaction; General procedure: For each reaction, a mixture consisting of the correspondingalkyne or aniline (calkyne = 0.3 M, caniline = 0.5 M) in CH2Cl2 was preparedand carefully homogenized. For small-scale reactions, 5 mLof the starting solution was pumped through the reactor underthe appropriate conditions, and elution of the starting materialwas continued by washing with CH2Cl2 for several additional minutes.In optimization experiments, the system was equilibrated for20 min between two reactions by pumping CH2Cl2 at a flow rate of0.5 mL min1. For the large-scale syntheses, the product collectionwas simply continued for an extended period of time, the conversionand selectivity being determined in every hour. The crudeproducts were checked by HPLC and NMR to determine conversionand selectivity. If necessary, column chromatographic purificationwas carried out with mixtures of n-hexane/EtOAc as eluent.
94% With oxygen In dimethyl sulfoxide at 20℃; for 24h;
93% With piperidine; copper(l) chloride In toluene at 60℃;
90% With copper(l) iodide; 4-(1,2,5,6-di-O-isopropylidene-3-O-methyl-α-D-glucofuranos-3-yl)-1H-[1,2,3]-triazole; potassium carbonate In N,N-dimethyl-formamide at 20℃; for 10h;
88% With N,N,N,N,-tetramethylethylenediamine; copper(I) triflate; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 100℃; Reactor;
87% With piperidine; copper(l) chloride In toluene at 60℃; for 5h;
81% With bis-triphenylphosphine-palladium(II) chloride; 1-(2-pyridylethynyl)-2-(2-thienylethynyl)benzene; triethylamine In acetonitrile at 20℃; for 21h;

  • 46
  • [ 14918-21-9 ]
  • [ 1101-41-3 ]
  • 5-cyano-2-(diphenylphosphinyl)-1-pentene [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% Stage #1: 5-hexynonitrile; Tetraphenyldiphosphin With diethylmethylsilane In benzene-d6 at 80℃; for 18h; Stage #2: With air In benzene-d6 Further stages.;
50% Stage #1: 5-hexynonitrile; Tetraphenyldiphosphin In benzene-d6 at 80℃; for 8h; Stage #2: With air Further stages.;
  • 47
  • <i>N</i>-(5,6-dihydro-4<i>H</i>-pyran-3-yl)-benzamide [ No CAS ]
  • [ 14918-21-9 ]
  • 4-pent-4-ynyl-2-phenyl-7,8-dihydro-6H-pyranol[3,2-d]pyrimidine [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With 2-chloropyridine In dichloromethane at -78 - 23℃;
77% With 2-chloropyridine; trifluoromethylsulfonic anhydride In dichloromethane at 23℃; for 1h;
  • 48
  • [ 6921-28-4 ]
  • [ 14918-21-9 ]
  • C12H14N2*HCl [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: dipropargylamine With pyridine In dichloromethane at 20℃; for 12h; Stage #2: 5-hexynonitrile In ethanol; dichloromethane at 60℃; for 48h; Stage #3: With hydrogenchloride In methanol; dichloromethane at 20℃; for 1h; Further stages.;
  • 49
  • [ 14918-21-9 ]
  • [ 102169-54-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 41 percent / LiAlH4 / diethyl ether / Heating 2: 91 percent / HCl / diethyl ether
  • 50
  • [ 660449-16-1 ]
  • [ 14918-21-9 ]
  • [ 660451-99-0 ]
YieldReaction ConditionsOperation in experiment
84% With triethylamine In tetrahydrofuran at 80℃; for 0.166667h; 124.1 Example 124; [6- [3- (AMINOMETHYL)-2-ISOBUTYL-4- (4-METHYLPHENYL)] quinolin-6- yl] hexanoic acid dihydrochloride 1) To a solution of [3-[(TERT-BUTOXYCARBONYL)] amino] methyl}-2- isobutyl-4- (4-methylphenyl) quinolin-6-yl trifluoromethanesulfonate (3.03 g, 6.13 mmol), copper iodide (176 mg, 0.920 mmol) and hex-5-ynenitrile (2.86 g, 30.7 mmol) in tetrahydrofuran (30 ml) -triethylamine (10 ml) was added dichlorobistriphenylphosphinepalladium (431 mg, 0.613 mmol), and the mixture was stirred under an argon atmosphere at [80°C] for 10 min. The reaction mixture was diluted with ethyl acetate, washed with saturated aqueous ammonium chloride solution, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give black crystals. The crystals were recrystallized from ethyl acetate- n-hexane to give tert-butyl [( [6- (5-CYANOPENT-1-YN-1-YL)-2-] [ISOBUTYL-4- (4-METHYLPHENYL) QUINOLIN-3-YL] METHYL}] carbamate (2.56 g, yield [84%)] as white crystals. Subsequently, tert- butyl [1 [6- (5-CYANOPENT-1-YN-1-YL)-2-ISOBUTYL-4- (4-] methylphenyl) quinolin-3-yl] methyl} carbamate (2.56 g, 5.17 mmol) and 10% palladium-carbon (550 mg) were suspended in a mixed solvent of ethanol (200 ml) -tetrahydrofuran (35 ml) and the mixture was stirred under a hydrogen atmosphere at room temperature for 3.5 hrs. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to give tert-butyl [{ [6- (5-CYANOPENTYL)-2-ISOBUTYL-4- (4-] methylphenyl) quinolin-3-yl] methyl} carbamate (2.37 g, yield 92%) as white crystals. [1H-NMR] [(CDC13) 8] : 1.02 (6H, d, J = 6.0 Hz), 1.41 (9H, s), 1.56- 1.69 (6H, m), 2.29 (2H, t, J = 6.0 Hz), 2.32-2. 39 [(1H,] m), 2.49 (3H, s), 2.64 (2H, t, J = 6.0 Hz), 2.95 (2H, d, J = 6.0 Hz), 4.24-4. 36 (3H, m), 7.05 [(1H,] d, J = 3. 0 Hz), 7.13 (2H, d, J = 9.0 Hz), 7.34 (2H, d, J = 6.0 Hz), 7.49 [(1H,] d, J = 9.0 Hz), 7.99 [(1H,] d, J = 9.0 Hz).
2.56 g With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 80℃; for 0.166667h; Inert atmosphere;
  • 51
  • [ 16352-18-4 ]
  • [ 14918-21-9 ]
  • [ 1009808-71-2 ]
YieldReaction ConditionsOperation in experiment
75% With acrylic acid methyl ester In toluene at 100℃; for 16h;
  • 52
  • [ 28903-71-1 ]
  • [ 14918-21-9 ]
  • Co(C20N4H8(C6H4OCH3)4)(C((CH2)3CN)CH2) [ No CAS ]
  • 53
  • [ 14918-21-9 ]
  • [ 954371-23-4 ]
YieldReaction ConditionsOperation in experiment
84% With sodium azide; triethylamine hydrochloride In toluene for 9h; Heating / reflux; A flask (100 mL) was charged with nitrile 92 (1.12 mL, 0.011 mol) and toluene (20 mL). Triethylamine hydrochloride (4.41 g, 0.032 mol) and sodium azide (2.06 g, 0.032 mol) were added to the solution and the resulting mixture was heated at reflux for 9 h. As the reaction progressed a black liquid formed at the bottom of the reaction vessel. The system was allowed to cool to room temperature and the reaction mixture was extracted with water (4 x 10 mL). Aqueous extracts were combined and acidified to a pη of 1 by adding concentrated hydrochloric acid. The aqueous phase was extracted with ethyl acetate (4 x 20 mL) and the combined organic extracts were dried over magnesium sulfate, filtered, and condensed in vacuo to afford a yellow oil that, when triturated with hexanes, solidified to low melting point solid (1.259 g, 84%): mp 24-26 0C. 1H NMR (300 MHz, DMSOd6) δ 3.31 (s, 1 H), 2.95 (t, J = 7.5 Hz, 2 H), 2.84 (t, J = 2.7 Hz, 1 H), 2.25 (dt, J = 7.2, 2.7 Hz, 2 H), 1.87 (p, J = 7.2 Hz, 2 H); CMS m/z (relative intensity) 137 (MH+, 100). Anal. (C6H8N4) C, H, N.
69% With sodium azide; triethylamine hydrochloride In toluene for 9h; Reflux;
  • 54
  • [ 929887-16-1 ]
  • [ 14918-21-9 ]
  • [ 67-63-0 ]
  • [ 1023756-93-5 ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: 2-(chlorodimethylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; 5-hexynonitrile In toluene at 20℃; for 1h; Stage #2: isopropyl alcohol With pyridine In toluene at 20℃; for 1h; Further stages.;
87% With pyridine In toluene Pd catalyst (1.0 mol%), borane and alkyne (1:1.2) in toluene stirred at room temp. for 1-3 h, treated with pyridine and iPrOH, stirred at room temp. for 1 h;
  • 55
  • 3-(4-iodo-phenyl)-4-hydroxy-6-oxo-6,7-dihydro-thieno[2,3-b]pyridine-5-carbonitrile [ No CAS ]
  • [ 14918-21-9 ]
  • 3-[4-(5-cyanopent-1-ynyl)phenyl]-4-hydroxy-6-oxo-6,7-dihydrothieno[2,3-b]pyridine-5-carbonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 3-(4-iodo-phenyl)-4-hydroxy-6-oxo-6,7-dihydro-thieno[2,3-b]pyridine-5-carbonitrile With copper(l) iodide; diethylamine In DMF (N,N-dimethyl-formamide) at 20℃; for 0.0833333h; Stage #2: 5-hexynonitrile In DMF (N,N-dimethyl-formamide) at 90℃; for 0.333333h; 193 EXAMPLE 193, 3-[4-(5-cyanopent-1-ynyl)phenyl]-4-hydroxy-6-oxo-6,7-dihydrothieno[2,3-b]pyridine-5-carbonitrile To a solution of 3-(4-iodo-phenyl)-4-hydroxy-6-oxo-6,7-dihydro-thieno[2,3-b]pyridine-5-carbonitrile (60 mg, 0.15 mmol) in 1.5 mL DMF was added diethylamine (0.16 mL, 1.5 mmol), followed by copper (I) iodide (trace), Pd(PPh3)Cl2 (3.5 mg, 0.005 mmol), and triphenylphosphine (12 mg, 0.04 mmol). The resulting mixture was stirred at rt for 5 min, after which hex-5-ynenitrile (50 μL, 0.5 mmol) was added. The reaction was then heated to 90° C. using microwave reactor for 20 min, filtered, concentrated and purified by reverse phase HPLC to give the titled compound. MS (ESI) m/e 358 (M-H)+; 1H NMR (300 MHz, DMSO-d6): δ 1.82-1.91 (m, 2H), 2.56 (t, J=7.12 Hz, 2H), 2.65 (t, J=7.12 Hz, 2H), 6.67 (s, 1H), 7.31 (d, J=8.48 Hz, 2H) 7.43 (d, J=8.48, 2H), 10.80 (s, 1H).
  • 56
  • [ 959150-64-2 ]
  • [ 14918-21-9 ]
  • [ 1216805-65-0 ]
  • 57
  • [ 26166-92-7 ]
  • [ 14918-21-9 ]
  • [ 1216805-75-2 ]
YieldReaction ConditionsOperation in experiment
64% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine In tetrahydrofuran Inert atmosphere; Reflux; chemoselective reaction;
  • 58
  • [ 14918-21-9 ]
  • [ 622-79-7 ]
  • [ 1207986-95-5 ]
YieldReaction ConditionsOperation in experiment
98% With bis-triphenylphosphano-copper(I)-butyrate In dichloromethane at 28℃; for 5h; regioselective reaction;
96% With Cu(II)Fe(III)-layered double hydroxide In dichloromethane at 100℃; Flow reactor; 2.4. general procedures for the CF reactions General procedure: To investigate the catalytic applicability of the as-prepared Cu(II)Fe(III)-LDH, a CF apparatus was assembled (Fig. S2). The system consisted of an HPLC pump (JASCO PU-880), which pro-vided a continuous stream of the reaction medium, a back pressurevalve and a stainless steel HPLC column (internal dimensions:4.6 × 50 mm) as catalyst bed, which encompassed the LDH material.The catalyst bed was combined with a stainless steel coil (with an internal diameter of 250 m) for preheating of the reaction mixture before entering the column. The catalyst bed and the preheating spiral were immersed into an oil bath for heating purposes.For the CF CuAAC reactions, 1 g of Cu(II)Fe(III)-LDH, Mg2Fe-LDH or copper powder (Sigma-Aldrich, average particle size: 200 m)was employed in the catalyst bed. A reaction mixture consisting of 1 equiv. of the azide and 1.5 equiv. of the alkyne in CH2Cl2 was prepared and homogenized carefully. The azide was applied in 0.085 M, which was the highest possible concentration without the precipitation of the resulting triazole in the reactor channel. If nec-essary, 0.04 equiv. of glacial acetic acid (AcOH) and/or 0.04 equiv.of N,N-diisopropylethylamine (DIEA) were added as additives. For small scale reactions, 5 mL of the starting solution was pumped through the reactor under the appropriate conditions, and elutionof the starting materials was continued by washing with CH2Cl2 for several additional minutes (depending on the set flow rate).Between two CF experiments, the system was equilibrated for 15 min by pumping CH2Cl2 at a flow rate of 0.5 mL min-1. For the large-scale synthesis, the concentration of the reactants was not varied, and 300 mL of the starting solution was pumped through the instrument. The crude products were checked by thin-layer chromatography with a mixture of n-hexane/EtOAc as eluent, and the solvent was evaporated in vacuo. If necessary, column chromatographic purification was carried out on silica gel with a mixture of n-hexane/EtOAc as eluent. To determine the residence time on the catalyst bed a solution of a dye was pumped through the filled cat-alyst column, and the time that elapsed between the first contact of the dye with the cartridge and the moment when the colored solution appeared at the outlet was measured.
95% With Cu/Fe In dichloromethane at 30℃; for 12h;
86% With 5 wt % Cu/Fe; acetic acid; N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; Flow reactor; regioselective reaction;
79% With RuH(η2-BH4)(CO)(PCy3)2 In tetrahydrofuran at 80℃; for 1.5h; Inert atmosphere; regioselective reaction;
71% With carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II) In tetrahydrofuran at 80℃; for 2h;
37% With [(diisopropyl malonamide)2Cu(acetonitrile)]BF4 at 20℃; for 1h; Inert atmosphere; Schlenk technique;

  • 59
  • [ 21087-29-6 ]
  • [ 14918-21-9 ]
  • [ 124-38-9 ]
  • [ 1253101-27-7 ]
YieldReaction ConditionsOperation in experiment
83% With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); potassium carbonate In N,N-dimethyl-formamide at 60℃; for 24h; Autoclave;
  • 60
  • [ 14918-21-9 ]
  • [ 1246224-47-4 ]
YieldReaction ConditionsOperation in experiment
94% With NBS; silver(I) nitrate In propan-2-one at 20℃; for 2h;
87% With NBS; silver(I) nitrate In propan-2-one at -78 - 20℃; for 15h; Inert atmosphere;
85% With NBS; silver(I) nitrate In propan-2-one for 4h; Schlenk technique;
78% With NBS; silver(I) nitrate In propan-2-one at 20℃;
71% With NBS; silver(I) nitrate In propan-2-one at 20℃; for 3h; Inert atmosphere;
With NBS; silver(I) nitrate In propan-2-one at 20℃; for 3h;
With NBS; silver(I) nitrate In propan-2-one at 20℃;
With NBS; silver(I) nitrate In propan-2-one at 20℃; for 4h;

  • 61
  • [ 14918-21-9 ]
  • [ 29427-58-5 ]
  • [ 122775-34-2 ]
  • [ 1248338-80-8 ]
  • 62
  • [ 14918-21-9 ]
  • [ 40106-58-9 ]
  • [ 1276690-57-3 ]
  • 63
  • [ 14918-21-9 ]
  • [ 622-79-7 ]
  • [ 1313994-74-9 ]
YieldReaction ConditionsOperation in experiment
53% With copper(ll) sulfate pentahydrate; D-glucose; sodium tartrate In methanol; water at 20℃; for 48h;
52% With copper(l) iodide; sodium hydroxide In methanol at -35℃; for 48h; Molecular sieve; Copper-catalyzed cycloadditions at low temperature. Typical procedure. A solution of the appropriate azide (2 mmol) in MeOH (3.0 mL) was added to a stirred mixture of the corresponding alkyne (2.1 mmol), a 0.5N solution of NaOH (0.5 mL, 0.25 mmol), 4A molecular sieves (0.05 g, 0.1 mmol) and CuI (0.019g, 0.1 mmol) in MeOH (2.0 mL). The reaction mixture was stirred at -35°C for 48h. BaCl2 (0.124 g, 0.6 mmol) was added, and the resulting mixture was stirred at -35°C for 30 min. The reaction mixture was warmed to room temperature and filtered through celite, and the solvent was removed in vacuo. The final product was purified by column chromatography (SiO2, hexane/AcOEt 8:2).
  • 64
  • [ 14918-21-9 ]
  • [ 124-38-9 ]
  • [ 1264749-65-6 ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: 5-hexynonitrile; carbon dioxide With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With hydrogenchloride In dichloromethane; water Table 5. Copper catalyzed carboxylation of terminal alkynes with CCv Reaction conditions: for LI, CuCl (2.0 mol %), TMEDA, 1.5 mol %; for L12, P(NHC)(NHC-Cu), 5 mol%; alkynes (2.0 mmol), base (2.4 mmol), C02 (1 atm), DMF (4 mL), r.t.. M monocarboxylic acid was obtained. General Procedure for Carboxylation of the Terminal Alkynes (lb as Example); CuCl (4.0 mg, 0.04 mmol, 2.0 mol %), TMEDA (3.5 mg, 0.03 mmol, 1.5 mol %), and K2C03 or Cs2C03 (2.4 mmol) were added to the DMF (4 mL) in the reaction tube (10 mL). C02 and 2 mmol of terminal alkynes (la, 204 mg) were introduced into the reaction mixture under stirring. The reaction mixture was stirred at room temperature (about 24 °C) for 16 hours. After completion of the reaction, the reaction mixture was transferred to the potassium carbonate solution (2 N, 5 mL) and the mixture was stirred for 30 mins. The mixture was extracted with dichloromethane (3 >< 5 mL) and the aqueous layer was acidified with concentrated HC1 to PH = 1 , then extracted with diethyl ether (3 χ 5 mL) again. The combined organic layers were dried with anhydrous Na2S04, filtered and the solution was concentrated in vacuum affording pure product. Element analysis calcd (%) for lb [C9H602 (146.0)]: C 73.97, H 4.14; found: C 73.82, H 4.07. Data for 1H and 13C NMR of acids were all conducted in d - DMSO or CDC13 and consistent with the data in reported literatures.
  • 65
  • potassium (4-iodophenyl)trifluoroborate [ No CAS ]
  • [ 14918-21-9 ]
  • potassium 4-(4-(3-cyanopropyl)-1H-1,2,3-triazol-1-yl)phenyltrifluoroborate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With sodium azide; caesium carbonate; copper(I) bromide; N,N`-dimethylethylenediamine In dimethyl sulfoxide at 90℃; for 1.5h; Atmospheric conditions; regiospecific reaction; 4.2. General procedure I (one-pot 1,3-dipolar cycloaddition reactions) Table 1 General procedure: To a solution of potassium haloaryltrifluoroborate (0.25 mmol), NaN3 (16.3 mg, 0.25 mmol), CuBr (3.6 mg, 10 mol %), Cs2CO3 (81.5 mg, 0.25 mmol), and N,N'-dimethylethylenediamine (4.4 mg, 20 mol %) in DMSO-d6 (1 mL) was added corresponding alkyne (0.28 mmol, 1.1 equiv) under atmospheric conditions. The reaction mixture was heated in an oil bath at 90 °C until the 1H NMR (in DMSO-d6) indicated completion of the reaction (see Table 1). After completion of the reaction, the solvent was removed in vacuum at 60-70 °C. The residual product was dissolved in dry acetone (3 mL), and the insoluble salts were removed by filtration through Celite. The solvent was concentrated on a rotary evaporator. The addition of Et2O led to the precipitation of the product. The product was filtered and dried in vacuum to afford the desired pure product.
  • 66
  • [ 14918-21-9 ]
  • [ 618-31-5 ]
  • [ 109-89-7 ]
  • [ 1333223-28-1 ]
YieldReaction ConditionsOperation in experiment
74% With triethylamine; copper(l) chloride In acetonitrile at 20℃; for 36h; Sealed vial; Typical procedure for the production of propargyl amines (Table 2, entry 1) General procedure: A mixture of tert-butylacetylene (1.0 mmol, 82 mg), benzal bromide (1.5 mmol, 250 mg), diethylamine (2.0 mmol, 146 mg), Et3N (1.0 mmol, 101 mg) and CuCl (10.0 mg, 10.0 mol %) were loaded in a sealed reaction vial (10 mL) with 2 mL of CH3CN. After stirring at room temperature for 36 h, the reaction mixture was diluted with H2O (20 mL), extracted with Et2O (2 × 10 mL), dried over Na2SO4 and concentrated to give the crude product which was further purified by column chromatography on silica gel (CH2Cl2) to afford the corresponding propargyl amine. All products gave satisfactory spectroscopic data.
  • 67
  • [ 14918-21-9 ]
  • [ 329976-80-9 ]
  • [ 1345981-07-8 ]
YieldReaction ConditionsOperation in experiment
56% With boron trifluoride diethyl etherate; copper diacetate In diethyl ether; toluene at 20℃; for 15h; 4.4. General procedure for amide synthesis General procedure: To a solution of copper (II) acetate (180 mg, 1 mmol) and potassium organotrifluoroborate (1 mmol) in toluene (2 mL) was added nitrile (10 mmol). Boron trifluoride (in solution in ether, ca. 48% BF3) was then added. The reaction media was stirred 15 h at room temperature. The reaction media was poured in 10 mL of water and extracted with ethyl acetate (3×5 mL). The combined organic layers were washed with brine (10 mL) and dried over MgSO4, filtered, and concentrated under reduce pressure. The crude was purified by chromatography on silica gel.
  • 68
  • [ 14918-21-9 ]
  • [ 1067-52-3 ]
  • [ 793719-65-0 ]
YieldReaction ConditionsOperation in experiment
77% In tetrahydrofuran Bu3SnOMe (1.2 mmol) and NC(CH2)3CCH (1 mmol) stirred at room temp. for 3h in presence of ZnBr2 catalyst (0.05 mmol), quenched by H2O; extracted with Et2O, organic layer sepd., dried (MgSO4), volatiles evapd., residue diluted with AcOEt, washed with NH4F, ppt. filtered off, filtrate dried (MgSO4), volatiles evapd.; detd. by (1)H NMR;
44% With zinc dibromide In tetrahydrofuran at 20℃; for 3h; Inert atmosphere; Preparation of 5-(tributylstannyl)hex-5-enenitrile (1i)1 To a suspended solution of ZnBr2 (4.58 mol%, 0.228 g) and 5-cyano-1-pentyne (22.1 mmol, 2.06 g) in THF (40 mL) was added tributyl(methoxy)stannane (23.0 mmol, 7.38 g). The mixture was stirred for 3 h at room temperature, and then quenched by NH4Faq (10%, 50 mL). The obtained white precipitate was filtered off, and the filtrate was extracted with Et2O (3 x 10 mL) and dried over MgSO4. The volatiles were removed under reduced pressure to give a crude product. It was purified by distillation under reduced pressure to give the pure product (3.69 g, 44%). The analytical data agreed withthe previous report.3 1H, 13C, and 119Sn NMR charts are listed below.
  • 69
  • [ 591-50-4 ]
  • [ 14918-21-9 ]
  • [ 152858-50-9 ]
YieldReaction ConditionsOperation in experiment
90% With C16H20Cl2N2O2Pd; potassium hydroxide In water; acetonitrile at 60℃; for 4h; 31. General procedure for Sonogashira coupling reaction General procedure: In a 10 mL round bottom flask, the palladium complex (0.010 mmol) was dissolved in acetonitrile (2 mL). Aryl halide (1.0 mmol), alkyne (1.2 mmol), KOH (2.00 mmol) and distilled water (2 mL) were added. The mixture was stirred at room temperature (or 60° C) for the required time. After reaction completion, the product was extracted with ethyl acetate (3x5 mL). The combined organic layers were dried with anhydrous sodium sulfate. The product was analyzed with GC and GC-MS. The product was purified using column chromatography with hexane-ethyl acetate as eluent. The characterization data were in entire agreement with the previously reported literature.32-39
89% With dichlorido[2,2'-(4-methylbenzene-1,2-diyl)bis(4,4-dimethyl-4,5-dihydro-1,3-oxazole)-N,N']palladium(II); potassium hydroxide In water; acetonitrile at 60℃; for 4h; General procedure: Appropriate palladium complex was dissolved in acetonitrile. Aryl halide, alkyne, KOH and distilled water were added. The mixture was stirred at room temperature (or 60°C) for the required time.
89% With copper(l) iodide; 4-(1,2,5,6-di-O-isopropylidene-3-O-methyl-α-D-glucofuranos-3-yl)-1H-[1,2,3]-triazole; potassium carbonate In N,N-dimethyl-formamide at 130℃; for 20h; Sealed tube;
85% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine at 85℃; for 12h; Schlenk technique; Inert atmosphere;
84% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 12h; Inert atmosphere; regioselective reaction;
80% With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine at 85℃; for 12h; Inert atmosphere; Sealed tube;
70% With 1,2-bis(thiophen-2-ylethynyl)benzene; bis-triphenylphosphine-palladium(II) chloride; triethylamine In acetonitrile at 20℃; for 17h; Inert atmosphere;

  • 70
  • [ 14918-21-9 ]
  • [ 98-88-4 ]
  • [ 1366425-32-2 ]
YieldReaction ConditionsOperation in experiment
86% With bis(benzonitrile)palladium(II) dichloride; henicosafluorodecyldiphenylphosphine; triethylamine In toluene at 20℃; for 1h; Inert atmosphere;
82% With bis-triphenylphosphine-palladium(II) chloride; 1-(2-pyridylethynyl)-2-(2-thienylethynyl)benzene; triethylamine In toluene at 40℃; for 5h; Inert atmosphere; General Procedure for the Coupling Reactions General procedure: Under N2 atmosphere, PdCl2(PPh3)2 (7.0 mg, 0.010 mmol), 3 (2.9 mg, 0.010 mmol), toluene (1.5 mL), acid halide 4 (0.60 mmol), terminal acetylene 5 (0.50 mmol), and NEt3 (0.20 mL, 1.7 mmol) were added into a 10 mL two-necked round-bottomed flask equipped with a condenser in this order. After the mixture was stirred at 40 oC for 5 h, 2 N NaOH aqueous solution (2.0 mL) was added and the reaction mixture was stirred for 30 min at ambient temperature. After addition of H2O (10 mL), the resulting mixture was extracted with Et2O (10 mL x 2) and the organic layer was washed with brine, dried over MgSO4. After removal of the solvent in vacuo, purification was performed by Preparative TLC on silica gel (Wakogel B-5F) using AcOEt and Hexanes as eluent to give the coupling product 6. Identification was conducted by 1H NMR, 13C NMR, and GC-MS (EI). Note: In the reaction of 9i and 9j, the resulting mixture was quenched with H2O (2 mL) instead of 2N NaOH solution.
  • 71
  • [ 14918-21-9 ]
  • [ 1370022-89-1 ]
  • [ 1370022-96-0 ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: ethyl 5-(3-chlorophenyl)-4-iodo-1H-pyrazole-3-carboxylate With copper(l) iodide; palladium 10% on activated carbon; triethylamine; triphenylphosphine In ethanol at 25 - 30℃; for 0.5h; Inert atmosphere; Stage #2: 5-hexynonitrile In ethanol at 20 - 70℃; Inert atmosphere; General procedure for the preparation of compound 3 General procedure: A mixture of ethyl 5-(3-chlorophenyl)-4-iodo-1H-pyrazole-3-carboxylate (1) (0.80 mmol), 10% Pd/C (0.02 mmol), PPh3 (0.15 mmol), CuI (0.03 mmol), and triethylamine (2.40 mmol) in ethanol (5 mL) was stirred at 25-30 °C for 30 min under nitrogen. The terminal alkyne (2) (1.2 mmol) was added, and the mixture was initially stirred at room temperature for 1 h and then at 70 °C for 8-9 h. After completion of the reaction, the mixture was cooled to room temperature, diluted with EtOAc (50 mL), and filtered through celite. The organic layers were collected, washed with water (3 × 30 mL), dried over anhydrous Na2SO4, filtered, and concentrated. The crude residue was purified by column chromatography on silica gel using hexane/ethyl acetate to afford the desired product.
  • 72
  • [ 14918-21-9 ]
  • [ 1370022-90-4 ]
  • [ 1370023-00-9 ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: ethyl 5-(3-chlorophenyl)-4-iodo-1-methyl-1H-pyrazole-3-carboxylate With copper(l) iodide; palladium 10% on activated carbon; triethylamine; triphenylphosphine In ethanol at 25 - 30℃; for 0.5h; Inert atmosphere; Stage #2: 5-hexynonitrile In ethanol at 20 - 70℃; Inert atmosphere; General procedure for the preparation of compound 3 General procedure: A mixture of ethyl 5-(3-chlorophenyl)-4-iodo-1H-pyrazole-3-carboxylate (1) (0.80 mmol), 10% Pd/C (0.02 mmol), PPh3 (0.15 mmol), CuI (0.03 mmol), and triethylamine (2.40 mmol) in ethanol (5 mL) was stirred at 25-30 °C for 30 min under nitrogen. The terminal alkyne (2) (1.2 mmol) was added, and the mixture was initially stirred at room temperature for 1 h and then at 70 °C for 8-9 h. After completion of the reaction, the mixture was cooled to room temperature, diluted with EtOAc (50 mL), and filtered through celite. The organic layers were collected, washed with water (3 × 30 mL), dried over anhydrous Na2SO4, filtered, and concentrated. The crude residue was purified by column chromatography on silica gel using hexane/ethyl acetate to afford the desired product.
  • 73
  • [ 14918-21-9 ]
  • [ 52372-89-1 ]
  • [ 1366610-41-4 ]
YieldReaction ConditionsOperation in experiment
68% With allyl(cyclopentadiene)palladium(II); triethylphosphine In tert-Amyl alcohol at 130℃; for 18h; Inert atmosphere; stereoselective reaction; Reaction of 1a with 2A (a typical procedure in ethylbenzene) General procedure: CpPd(p-allyl) (10 mg, 0.050 mmol), ethylbenzene (2.0 mL), PEt3 (1 M THF solution, 0.10 mL, 0.10 mmol), 2A (0.10 mL, 1.0 mmol) and 1a (0.29 g, 1.0 mmol) were placed in a 25 mL Schlenk tube and were heated at 130 °C for 6 h. Tetradecane (50 mL, internal standard) was added and the mixture was analyzed by GC. Then, volatiles were removed in vacuo and the resulting mixture was analyzed by 1H NMR in CDCl3 after addition of 1,1,2,2-tetrachloroehtane (20 μL, 0.19 mmol, internal standard). After evaporation of the mixture, the residue was subjected to preparative TLC (silica gel, toluene/ethyl acetate = 6/1) four times to isolate basically pure (E)-3aA (pale yellow oil, 0.28 g, 0.70 mmol, 70%). An analytically pure colorless solid was obtained by preparative HPLC.
  • 74
  • [ 14918-21-9 ]
  • [ 52372-89-1 ]
  • [ 1366610-41-4 ]
  • [ 1366610-42-5 ]
YieldReaction ConditionsOperation in experiment
1: 41% 2: 13 %Spectr. With allyl(cyclopentadiene)palladium(II); triethylphosphine In ethylbenzene at 130℃; for 18h; Inert atmosphere; stereoselective reaction; Reaction of 1a with 2A (a typical procedure in ethylbenzene) General procedure: CpPd(p-allyl) (10 mg, 0.050 mmol), ethylbenzene (2.0 mL), PEt3 (1 M THF solution, 0.10 mL, 0.10 mmol), 2A (0.10 mL, 1.0 mmol) and 1a (0.29 g, 1.0 mmol) were placed in a 25 mL Schlenk tube and were heated at 130 °C for 6 h. Tetradecane (50 mL, internal standard) was added and the mixture was analyzed by GC. Then, volatiles were removed in vacuo and the resulting mixture was analyzed by 1H NMR in CDCl3 after addition of 1,1,2,2-tetrachloroehtane (20 μL, 0.19 mmol, internal standard). After evaporation of the mixture, the residue was subjected to preparative TLC (silica gel, toluene/ethyl acetate = 6/1) four times to isolate basically pure (E)-3aA (pale yellow oil, 0.28 g, 0.70 mmol, 70%). An analytically pure colorless solid was obtained by preparative HPLC.
  • 75
  • [ 14918-21-9 ]
  • [ 94064-00-3 ]
  • [ 1408230-61-4 ]
YieldReaction ConditionsOperation in experiment
90% Stage #1: 3-chloro-N-p-tolylquinoxalin-2-amine With copper(l) iodide; 10% Pd/C; triethylamine; triphenylphosphine In toluene at 25 - 30℃; for 0.333333h; Inert atmosphere; Stage #2: 5-hexynonitrile In toluene at 20 - 100℃; for 4.2h; Inert atmosphere; General Procedure for the preparation 1,2-disubstitutedpyrrolo[2,3-b]quinoxalines (3) General procedure: A mixture of 3-Chloro-N-aryl quinoxalin-2-amine (1) (1.0 mmol), 10% Pd/C (0.028 mmol), PPh3 (0.15 mmol), CuI (0.052 mmol), and triethylamine (2.5 mmol) in toluene (5 mL) was stirred at 25-30 °C for 20 min under nitrogen. To this mixture was added a terminal alkyne (2) (1.8 mmol) slowly. The mixture was then stirred at room temperature for 15 min and then at 95-100 °C for 3-5 h. After completion of the reaction the mixture was cooled to room temperature, diluted with EtOAc (50 mL), and filtered through celite. The organic layers were collected, washed with water (3 × 30 mL), dried over anhydrous Na2SO4, filtered, and concentrated. The crude residue was purified by column chromatography on silica gel (230-400 mesh) using hexane/ethyl acetate to afford the desired product.
  • 76
  • [ 30884-53-8 ]
  • [ 14918-21-9 ]
  • [ 1400420-69-0 ]
YieldReaction ConditionsOperation in experiment
50% With copper(l) iodide; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 10h; General procedure for the synthesis of Triazolbenzo[d]thiazoles General procedure: 1a-c/2a-c or 14 (0.77 mmol) was added to a dry round-bottom flask in THF (7 ml) followed by CuI (0.77 mmol), DIPEA (2.31 mmol) and alkyne (1.16 mmol). The solution was allowed to stir at room temperature until starting material was consumed 1- 10 hrs. The reaction mixture was concentrated, purified by flash chromatography to afford the targeted Triazolbenzo[d]thiazoles.
  • 77
  • [ 14918-21-9 ]
  • [ 6635-39-8 ]
  • [ 1400420-43-0 ]
YieldReaction ConditionsOperation in experiment
64% With copper(l) iodide; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; General procedure for the synthesis of Triazolbenzo[d]thiazoles General procedure: 1a-c/2a-c or 14 (0.77 mmol) was added to a dry round-bottom flask in THF (7 ml) followed by CuI (0.77 mmol), DIPEA (2.31 mmol) and alkyne (1.16 mmol). The solution was allowed to stir at room temperature until starting material was consumed 1- 10 hrs. The reaction mixture was concentrated, purified by flash chromatography to afford the targeted Triazolbenzo[d]thiazoles.
  • 78
  • [ 2516-40-7 ]
  • [ 14918-21-9 ]
  • [ 1440509-61-4 ]
  • 79
  • [ 14918-21-9 ]
  • [ 939759-26-9 ]
  • benzyl 3-(5-cyanopent-1-yn-1-yl)azetidine-1-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% Stage #1: benzyl 3-iodoazetidine-1-carboxylate With bis(1,5-cyclooctadiene)nickel (0); copper(l) iodide; lithium tert-butoxide; 2,6-bis(4,5-dihydrooxazol-2-yl)pyridine In 1,2-dimethoxyethane; N,N-dimethyl acetamide for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: 5-hexynonitrile In 1,2-dimethoxyethane; N,N-dimethyl acetamide at 20℃; for 24h; Inert atmosphere; Schlenk technique;
  • 80
  • [ 14918-21-9 ]
  • [ 1637649-81-0 ]
  • [ 1637649-86-5 ]
YieldReaction ConditionsOperation in experiment
94% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In N,N-dimethyl-formamide for 6h; Inert atmosphere; Heating; General Procedure for the synthesis of 7-H/substituted 3-phenylsulfonyl-3,6-dihydropyrrolo[3,2-e]indazoles (12a-h) General procedure: A mixture of 10 (0.25 g, 0.5 mmol), the alkyne 11a-h (0.7mmol), Pd(Ph3P)2Cl2 (35 mg; 10 mol %), CuI (19 mg; 10 mol %) and Et3N (0.7 mL; 5 mmol) inDMF (3 mL) was stirred at 100 °C in argon atmosphere until (5-10 h) the reaction was complete(the reaction darkened in color). It was cooled to rt, filtered through a bed of Celite and washedwith EtOAc (3 × 15 mL). The combined organic layer was washed with brine and then H2O, dried (Na2SO4) and the solvent distilled off. The residue obtained was purified by CC andcrystallized from EtOAc/PE mixture.
  • 81
  • [ 104-92-7 ]
  • [ 14918-21-9 ]
  • 6-(4-methoxy-phenyl)-hex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With dichloro bis(acetonitrile) palladium(II); N-Methyldicyclohexylamine; di-tert-butyl(4-sulfonatobenzyl)phosphonium In water; acetonitrile at 80℃; Inert atmosphere; Glovebox; General procedure for Sonogashira coupling of alkylacetylenes General procedure: In a nitrogen filled glove box, PdCl2(CH3CN)2 (3.25 mg, 0.010025 mmol) and 2a (11.8 mg, 0.0375 mmol) or 2b (17.7 mg, 0.0375 mmol) were measured into a 1 dram vial containing a small stir bar. The vial was sealed with a screw cap and septum and removed from the glovebox before adding Cy2NMe (235 μL, 1.10 mmol), aryl halide (1.00 mmol), alkyl acetylene (1.10 mmol), and 1:1 water/acetonitrile (2 mL). The reaction vial was placed in a preheated oil bath at 80 °C and stirred until it reached completion as determined by gas chromatography (2-12 h). Upon completion, the reaction mixture was taken into diethyl ether, washed with brine solution, dried with anhydrous magnesium sulfate, and filtered. The excess organic solvent was removed under reduced pressure, and the crude residues were taken into methylene chloride and evaporated onto silica gel under reduced pressure. Once dry, the silica gel mixture was used in column chromatography.
78% With dichloro bis(acetonitrile) palladium(II); N-Methyldicyclohexylamine; di-tert-butyl(4-sulfonatobenzyl)phosphonium In water; acetonitrile at 80℃; Inert atmosphere; Glovebox; General procedure for Sonogashira coupling of alkylacetylenes General procedure: In a nitrogen filled glove box, PdCl2(CH3CN)2 (3.25mg, 0.010025mmol) and 2a (11.8mg, 0.0375mmol) or 2b (17.7mg, 0.0375mmol) were measured into a 1 dram vial containing a small stir bar. The vial was sealed with a screw cap and septum and removed from the glovebox before adding Cy2NMe (235μL, 1.10mmol), aryl halide (1.00mmol), alkyl acetylene (1.10mmol), and 1:1 water/acetonitrile (2mL). The reaction vial was placed in a preheated oil bath at 80°C and stirred until it reached completion as determined by gas chromatography (2-12h). Upon completion, the reaction mixture was taken into diethyl ether, washed with brine solution, dried with anhydrous magnesium sulfate, and filtered. The excess organic solvent was removed under reduced pressure, and the crude residues were taken into methylene chloride and evaporated onto silica gel under reduced pressure. Once dry, the silica gel mixture was used in column chromatography.
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); dimethyl(propan-2-yl)silane; palladium diacetate; lithium tert-butoxide; dicyclohexyl(2'-methoxy[1,1'-biphenyl]-2-yl)phosphine In toluene at 45℃; for 3h; Glovebox; Inert atmosphere;
  • 82
  • [ 14918-21-9 ]
  • [ 5048-19-1 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogen In toluene at 20℃; for 12h; Autoclave; chemoselective reaction;
90% With triethanolamine; hydrogen In water; acetonitrile at 55.84℃; for 5h; Sealed tube; Inert atmosphere; UV-irradiation; diastereoselective reaction; 2.3 Photocatalytic hydrogenation of alkynes in an aqueous acetonitrile suspension of DHN/TiO2-Cu under visible light irradiation General procedure: In a typical run, prepared DHN/TiO2-Cu (50mg) was suspended in water-acetonitrile (1:9) solution (5cm3) containing alkyne (ca. 50μmol) and triethanolamine (TEOA, 150μmol) as a sacrificial reagent in a test tube, and the test tube was sealed with a rubber septum under argon and then photoirradiated with visible light of the two blue LEDs (420-530nm, 29.0 and 56.8mWcm-2, Hayashi Watch Works, Tokyo) from two directions with magnetic stirring at 329K. The emission spectra of light from two blue LEDs are shown in Fig. S1. The amount of H2 was measured with an FID-type gas chromatograph (GC-8A, Shimadzu, Kyoto) equipped with an MS-5A column. After the suspension had been filtered to remove the catalyst, the amounts of PP unreacted and hydrogenation products (cis-alkene, trans-alkene and alkane) formed in the liquid phase were determined with an FID-type gas chromatograph (GC-2025, Shimadzu) equipped with a DB-1 column. Toluene was used as an internal standard substance. Toluene (5mm3), water (1cm3) and diethyl ether (3cm3) were added to the reaction solution (2cm3). After the mixture had been stirred for 10min, the diethyl ether phase of the reaction solution was analyzed. The amounts of alkyne, alkene and alkane were determined from the ratios of the peak areas of these products to the peak area of toluene.
96 %Spectr. With formic acid; Au9924Ag0.76; triethylamine In N,N-dimethyl-formamide at 70℃; for 4h; Inert atmosphere; Green chemistry; chemoselective reaction;
With Ru(CH9BBNMepi)PPh<SUB>3</SUB>; hydrogen In benzene-d6 at 80℃; for 2h; Inert atmosphere; Schlenk technique;
93 %Chromat. With hydrogen In ethanol at 20℃; for 1.7h; Schlenk technique; Sealed tube; chemoselective reaction;
With Dimethylphenylsilane; water In dimethyl sulfoxide at 70℃; for 0.333333h; Inert atmosphere; stereoselective reaction;
With isopropyl alcohol at 19.84℃; for 2h; Inert atmosphere; UV-irradiation; chemoselective reaction;
With hydrogen In isopropyl alcohol at 19.84℃; for 5h; Irradiation; 3.6. Reusability and applicability of Pd(at)Ag/TiO2 General procedure: Table 6 shows the results of re-use of PdAg/TiO2 for hydrogenationof 4-octyne and use of PdAg/TiO2 for hydrogenation of other alkynes. After the first use (Entry 1), PdAg/TiO2 still showed high performance for 4-octyne hydrogenation in the second and third uses (Entries 2 and3). cis-Selectivity was also achieved in hydrogenation of 2-hexyne (Entry4). PdAg/TiO2 also worked in hydrogenation of terminal alkynes to corresponding alkenes (Entries 5-7). We noted that PdAg/TiO2 wasnot active for a carbon-nitrogen triple bond (C- - -N) (Entries 6). Interestingly,a chloro group, which is typically a good leaving group, was preserved in hydrogenation of alkyne (Entries 7). Since Pd is very active for elimination of a chloro group from a hydrocarbon [10], this resultindicates that the Pd core was almost completely covered with the Ag shell. These results show a wide applicability of the PdAg/TiO2 photocatalystin hydrogenation of alkynes to alkenes.

  • 83
  • [ 14918-21-9 ]
  • [ 1214264-88-6 ]
  • [ 1067-52-3 ]
  • (E)-5-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)-6-(tributylstannyl)hex-5-enenitrile [ No CAS ]
  • C28H42BN3Sn [ No CAS ]
  • 84
  • [ 14918-21-9 ]
  • [ 102169-54-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: tris(pentafluorophenyl)borate / chloroform-d1 / 0.17 h / 25 °C / Inert atmosphere 2: hydrogenchloride; water / diethyl ether / 1 h / 20 °C
  • 85
  • [ 14918-21-9 ]
  • copper(l) chloride [ No CAS ]
  • (5-cyanopent-1-ynyl)copper [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With ammonium hydroxide In ethanol; water at 20℃; for 0.266667h; Inert atmosphere; 5 3.1.5. General method for the synthesis of cuprous acetylide(Table 3) General procedure: A solution of alkyne (1 equiv) in EtOH (0.3 M) was added slowlyover 1 min to a magnetically stirred solution of CuCl (1.2 equiv) in NH4OH (28%, 1.6 M). The mixture was stirred for 15 min uponwhich time the cuprous acetylide precipitated. H2O (100 mL per1 mL of alkyne) is added and the precipitate collected by vacuumfiltration, washed with NH4OH (5%, 25 mL per 100 mL ofalkyne 2) plus H2O (25 mL per 1 mL of alkyne 2) and dried ina vacuum desiccator overnight to give the cuprous acetylide as acoloured powder and which was used without need for furtherpurification. 3.1.5.5 (5-Cyanopent-1-ynyl)copper 42e Prepared using the general procedure for the synthesis of cuprous acetylides using 5-hexynenitrile (0.2 mL, 1.91 mmol). 5-Cyanopent-1-ynyl-copper 42e (102 mg, 1.09 mmol, 57%) was obtained as a yellow powder and used without further purification. Mp ⩾180 °C decomposes. IR (Neat, cm-1) 3343 (OH), 2941 (C-H), 2247 (C≡N), 1570, 1424, 901. Anal. Calcd for C6H6NCu: C, 46.29; H, 3.89; N, 9.00. Found: C, 46.34; H, 3.77; N, 9.01.
  • 86
  • [ 14918-21-9 ]
  • 2-(azidomethyl)-1-bromo-3,4-dihydronaphthalene [ No CAS ]
  • 6,7-dihydro-5H-benzo[g][1,2,3]triazolo[5,1-a]isoindole-11-butanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% Stage #1: 2-(azidomethyl)-1-bromo-3,4-dihydronaphthalene With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; Stage #2: 5-hexynonitrile In N,N-dimethyl-formamide at 60℃; for 8h; Inert atmosphere; General procedure for the synthesis of annulated 1,2,3-triazoles 1a-1n General procedure: A mixture of 2-/1-azidomethyl-1-/2-bromodihydro-naphthalenes/-arene/cycloalkenes (0.5 mmol), 57 mg Pd(PPh3)4 (10 mol%), 15 mg CuI (15 mol%), and 0.3 cm3 Et3N (2.5 mmol) in 2 cm3 DMF was stirred at rt in argon atmosphere for 1 h. The alkyne 4 (1 mmol) was added to the above mixture and stirred at 60°C until the reaction was complete (8-12 h). It was then cooled to room temperature, filtered through a bed of Celite and washed with DCM (3*15 cm3). The combined organic layer was washed with saturated aq. NH4Cl, H2O, dried (anhydr. Na2SO4), and the solvent distilled off. The residue obtained was purified by column chromatography, followed by recrystallization from EtOAc-petroleum ether (60-80°C) mixture.
  • 87
  • [ 14918-21-9 ]
  • [ 951887-60-8 ]
YieldReaction ConditionsOperation in experiment
98% With hydrogenchloride; chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II); triphenylphosphine In diethyl ether; 1,2-dichloro-ethane at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique;
98% With C37H61AuClO2P; HCl·DMPU In nitromethane at 20℃; regioselective reaction;
80% With hydrogenchloride; 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; Au-TiO2 In N,N-dimethyl-formamide at 100℃; for 7h; regioselective reaction;
78% With 4-chloro-2-butanone; bis(1,5-cyclooctadiene)diiridium(I) dichloride; 2′-(dicyclohexylphophanyl)-N2,N2,N6,N6-tetramethyl[1,1′-biphenyl]-2,6-diamine In toluene at 80℃; for 5h; Inert atmosphere; Sealed tube; Glovebox;

  • 88
  • [ 110-66-7 ]
  • [ 14918-21-9 ]
  • C11H19NS [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With (N,N′-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene)Pd(acac)Cl; 3-isopropyl-6-methylcyclohexa-1,4-diene; triethylamine In neat (no solvent) at 100℃; for 8h; Green chemistry; regioselective reaction;
  • 89
  • [ 14918-21-9 ]
  • [ 624-38-4 ]
  • 6,6'-benzene-1,4-diylbishex-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With C16H20Cl2N2O2Pd; potassium hydroxide In water; acetonitrile at 60℃; for 12h; 31. General procedure for Sonogashira coupling reaction General procedure: In a 10 mL round bottom flask, the palladium complex (0.010 mmol) was dissolved in acetonitrile (2 mL). Aryl halide (1.0 mmol), alkyne (1.2 mmol), KOH (2.00 mmol) and distilled water (2 mL) were added. The mixture was stirred at room temperature (or 60° C) for the required time. After reaction completion, the product was extracted with ethyl acetate (3x5 mL). The combined organic layers were dried with anhydrous sodium sulfate. The product was analyzed with GC and GC-MS. The product was purified using column chromatography with hexane-ethyl acetate as eluent. The characterization data were in entire agreement with the previously reported literature.32-39
  • 90
  • [ 14918-21-9 ]
  • [ 79-19-6 ]
  • 5-(pent-4-yn-1-yl)-1,3,4-thiadiazol-2-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With trifluoroacetic acid at 85℃; for 6h; 7.1 Step 1 : 5-(pent-4-yn-l-yl)-l,3,4-thiadiazol-2-amine To a suspension of hydrazinecarbothioamide (538 mg, 5.91 mmol) in TFA (2.48 ml, 32.2 mmol) was added hex-5-ynenitrile (562 μ, 5.37 mmol) and the mixture was heated at 85 °C for 6 h. The mixture was cooled to RT, poured onto an ice-water mixture and brought to pH = 14 by stirring with NaOH (1.3 g, 32 mmol). The mixture was concentrated under reduced pressure, the residue was adsorbed onto a pad of Celite, and purified via S1O2 gel chromatography (0 to 15% MeOH in DCM) to give the title compound as a white solid (680 mg, 76%). MS (ES+) C7H9N3S requires: 167, found: 168 [M+H]+.
  • 91
  • [ 14918-21-9 ]
  • 6,6-dibromo-5-oxohexanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With N-Bromosuccinimide; perchloric acid In water; acetonitrile at 20℃; for 12h; Inert atmosphere; General procedure for the preparationof α,α-dibromoketones 5 General procedure: Acetonitrile (2 cm3/mmol), water (1 cm3/mmol), and HClO4 (10 mol %) was added to a mixture of alkyne 4(1.0 mmol) and NBS (2.5 mmol). The resultant mixture was stirred for the time indicated in Table 1. Then, thereaction mixture was diluted with Et2O (8 cm3/mmol) andwashed with a saturated solution of Na2CO3 (3 cm3/mmol),Na2S2O3 (3 cm3/mmol), water (3 cm3/mmol), and brine (3 cm3/mmol). The organic layer was dried over MgSO4,concentrated under reduced pressure and column chromatographyon silica gel afforded the a,a-dibromoketones 5.
  • 92
  • [ 14918-21-9 ]
  • [ 77897-23-5 ]
  • (S)-7-((S)-3-benzylmorpholino)-7-methylundec-5-ynedinitrile [ No CAS ]
  • 93
  • [ 14918-21-9 ]
  • [ 73183-34-3 ]
  • 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-hexenenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With bromobenzene; 2,2,2-trifluoroethanol; palladium diacetate; tricyclohexylphosphine In toluene at 80℃; for 12h; Inert atmosphere; regioselective reaction;
87% Stage #1: bis(pinacol)diborane With C23H37ClCuN; sodium t-butanolate In tetrahydrofuran at 22℃; for 0.0833333h; Inert atmosphere; Stage #2: 5-hexynonitrile In tetrahydrofuran; methanol at 22℃; for 12h; Inert atmosphere;
  • 94
  • [ 14918-21-9 ]
  • [ 4559-70-0 ]
  • 1,2-bis(diphenylphosphinyl)-5-hexanenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: Diphenylphosphine oxide With lithium tert-butoxide In tetrahydrofuran for 1h; Schlenk technique; Inert atmosphere; Stage #2: 5-hexynonitrile In tetrahydrofuran at 70℃; for 4h; Schlenk technique; Inert atmosphere; 2 Experimental procedures for the base-catalyzed double addition of phosphine oxidesto alkyn General procedure: In a Schlenk flask wereplaced diphenylphosphine oxide (0.2 mmol), and tBuOLi of THF solution (5 mol%, 0.01 mmol) in THF (0.15mL) under nitrogen. The mixture was stirred at ambient temperature for 1 h. Etynylbenzene(0.1 mmol) was added to the solution under nitrogen and the mixture was heatedat 70 °C for 4 h.
70% With air In N,N-dimethyl-formamide at 150℃; for 22h;
  • 95
  • [ 64-18-6 ]
  • [ 14918-21-9 ]
  • [ 147766-06-1 ]
YieldReaction ConditionsOperation in experiment
64% With o-phenylenebis(diphenylphosphine); bis(acetylacetonate)nickel; 2,2-dimethylpropanoic anhydride In 1,4-dioxane at 100℃; for 24h; Schlenk technique; Inert atmosphere; 20 Example 20: Preparation of 5-cyano-2-methylenepentanoic acid General procedure: The method as in Example 1, yield 64%, purity> 99%.In a 10mL Schlenk reaction tube (Hinwil Beijing GlassInstrument Co., F891410 reaction tube, the capacity of 10mL, 14/20 groundjoint) was added bis (acetylacetonate) Ni (5mol%, 6.5mg) and 1,2-bis (diphenylphosphino) benzene (7mol%, 15.6mg), was fully replaced with argon threetimes the air tube, under an argon atmosphere and then add 1ml of toluene,diphenyl acetylene (0.50mmol, 89.2mg), formic acid (1.1mmol, 50.6 mg) andpivalic anhydride (20mol%, 0.1mmol, 18.4mg); the reaction system was heated inan oil bath to 100 deg.] C and stirring was continued for 24 hours (using anIKA magnetic stirrer, the RCT basic, stirring speed of 500 rpm /minute). Aftercompletion of the reaction, the system was cooled to room temperature. Thereaction solution was diluted with ethyl acetate, and then the reactionsolution was diluted with a rotary evaporator and concentrated way (Buchi,Switzerland Ltd., by BUCHI Rotavapor R-3). Concentrated residue was purified bycolumn (Hinwil Beijing Glass Instrument Co., C383040C ball with sand boardstorage column, 5/20, φ30mm, effective length: 500ml) chromatography to givethe product.The product as a white solid, 109 mg, 98% yield,, purity>99%, eluent ethyl acetate: petroleum ether = 1: 50 to 1:10.Means of NMR obtained in Example 1 (E) -2,3- diphenyl-α, β-unsaturated carboxylic acid analysis, proton nuclear magnetic resonancespectrum thereof obtained as shown in FIG. 1; its 13C to give shown in FIGURE2.
  • 96
  • [ 14918-21-9 ]
  • [ 501-65-5 ]
  • [ 405198-82-5 ]
  • C27H22N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With copper(l) iodide; trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II); triethylamine; Trimethylacetic acid In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;
  • 97
  • [ 14918-21-9 ]
  • [ 4559-70-0 ]
  • 5-cyano-2-oxopentyl diphenylphosphinate [ No CAS ]
YieldReaction ConditionsOperation in experiment
69% With [bis(acetoxy)iodo]benzene; water In acetonitrile at 60℃; for 24h; 2.1. General procedure for the synthesis of a-hydroxyketonephosphates 3 General procedure: 2.1. General procedure for the synthesis of a-hydroxyketonephosphates 3 To a solution of diarylphosphine oxides 2 (0.5 mmol) inacetonitrile (3.0 mL) were added PhI(OAc)2 (1.25 mmol), H2O(2.0 mmol) and alkynes 1 (0.75 mmol). The reaction mixture wasthen stirred for 24 h at 60 8C in air. After the reaction, thesolvents were removed under vacuum. The residue was puriedby ash chromatography on silica gel using a mixture ofpetroleum ether and ethyl acetate (1:1) as eluent to give thedesired product 3.
  • 98
  • [ 50-00-0 ]
  • [ 14918-21-9 ]
  • [ 16486-68-3 ]
  • 7-(allyl(tert-butyl)amino)hept-5-yne-nitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With copper(I) bromide In toluene at 20℃; for 20h; Schlenk technique; Molecular sieve; Inert atmosphere;
  • 99
  • [ 123-75-1 ]
  • [ 14918-21-9 ]
  • [ 100-52-7 ]
  • 7-phenyl-7-(pyrrolidin-1-yl)hept-5-ynenitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With [CuCl{tBu-P(CH2CH=CH2)2}]4 In neat (no solvent) at 50℃; for 24h; Inert atmosphere; Darkness; Schlenk technique; General procedure for A3-coupling catalyzed by [CuCl{tBu-P(CH2CH=CH2)2}]4(2) General procedure: Under argon atmosphere, catalyst [CuCl{tBu-P(CH2CH = CH2)2}]4 2 (2.7 mg, 0.0025 mmol, 0.5 mol%), aldehyde (0.5 mmol), amine (0.55 mmol) and alkyne (0.75 mmol) were loaded in a screw-cap test tube equipped with a stirring bar. The mixture was stirred at 50 °C for 6 h and kept in the dark until completed the time of reaction. Then, the mixture was cooled, extracted with ether (3 * 5 mL) and dried over MgSO4. The mixture was filtrated, concentrated (1H NMR spectroscopy showed quantitative conversion of aldehyde) and the residue was purified by flash chromatography on silica gel (eluent: hexane/EtOAc = 3:1 V/V). The corresponding propargylamines were obtained as a racemic mixture in form of light-yellow oil. Reported yields are the average of at least two independent runs.
  • 100
  • [ 14918-21-9 ]
  • [ 99548-56-8 ]
  • C15H15NO2 [ No CAS ]
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