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[ CAS No. 2689-88-5 ] {[proInfo.proName]}

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Chemical Structure| 2689-88-5
Chemical Structure| 2689-88-5
Structure of 2689-88-5 * Storage: {[proInfo.prStorage]}
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Product Details of [ 2689-88-5 ]

CAS No. :2689-88-5 MDL No. :MFCD00101667
Formula : C13H16O4 Boiling Point : -
Linear Structure Formula :- InChI Key :MYZCCWFBKBDURM-UHFFFAOYSA-N
M.W : 236.26 Pubchem ID :231824
Synonyms :

Calculated chemistry of [ 2689-88-5 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 17
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.54
Num. rotatable bonds : 8
Num. H-bond acceptors : 4.0
Num. H-bond donors : 0.0
Molar Refractivity : 63.24
TPSA : 52.6 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) : -6.41 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.21
Log Po/w (XLOGP3) : 1.88
Log Po/w (WLOGP) : 1.3
Log Po/w (MLOGP) : 2.21
Log Po/w (SILICOS-IT) : 2.62
Consensus Log Po/w : 2.24

Druglikeness

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

Water Solubility

Log S (ESOL) : -1.96
Solubility : 2.58 mg/ml ; 0.0109 mol/l
Class : Very soluble
Log S (Ali) : -2.61
Solubility : 0.584 mg/ml ; 0.00247 mol/l
Class : Soluble
Log S (SILICOS-IT) : -1.87
Solubility : 3.16 mg/ml ; 0.0134 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 3.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 2.77

Safety of [ 2689-88-5 ]

Signal Word:Warning Class:
Precautionary Statements:P233-P260-P261-P264-P271-P280-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501 UN#:
Hazard Statements:H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 2689-88-5 ]

* 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 [ 2689-88-5 ]

[ 2689-88-5 ] Synthesis Path-Downstream   1~100

  • 1
  • [ 2689-88-5 ]
  • [ 4431-32-7 ]
YieldReaction ConditionsOperation in experiment
75.4% Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With potassium hydroxide for 15h; Reflux; Stage #2: With hydrogenchloride In water 6.b b. Synthesis of dipropargylmalonic acidDiethyl dipropargyl malonate (80 gm, 0.339 mol) was refluxed in 600 ml of 10% alcoholic potassium hydroxide overnight (15 hours). Solvent was removed in vacuo and the residue was acidified with 3N HCl. The residue was extracted with Et2O (2x 300ml). The combined extracts were dried over MgSO4, filtered, washed with Et2O and concentrated in vacuo to an oil. Placed on high vac (40 C) for 2 hours and let stand to afford dipropargylmalonic acid as an oil (46 gm, 75.4 % yield). Reaction was followed by GC.
With potassium hydroxide
With potassium hydroxide In methanol for 2h; Heating;
With hydrogenchloride; sodium hydroxide
With potassium hydroxide at 20℃; for 24h; Inert atmosphere;

  • 2
  • [ 17920-23-9 ]
  • [ 106-96-7 ]
  • [ 2689-88-5 ]
YieldReaction ConditionsOperation in experiment
With ethanol; sodium ethanolate
Stage #1: diethyl propargylmalonate With sodium hydride In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Stage #2: propargyl bromide In tetrahydrofuran at 20℃; Inert atmosphere;
  • 3
  • [ 106-96-7 ]
  • [ 105-53-3 ]
  • [ 2689-88-5 ]
YieldReaction ConditionsOperation in experiment
100% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil for 2h; Inert atmosphere; Cooling with ice; Stage #2: propargyl bromide In tetrahydrofuran; mineral oil at 0℃; Inert atmosphere;
98% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: propargyl bromide In tetrahydrofuran; toluene; mineral oil at 0 - 20℃; Inert atmosphere;
98% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: propargyl bromide In tetrahydrofuran; mineral oil at 0 - 20℃; Inert atmosphere;
94% With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water at 20℃; for 15h;
90% With sodium hydroxide for 16h;
90% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 2h; Stage #2: propargyl bromide In tetrahydrofuran; mineral oil at 0 - 20℃; for 24h;
90% With sodium hydride In tetrahydrofuran at 0℃; for 36h;
90% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: propargyl bromide In tetrahydrofuran at 20℃; for 36h; 4.3.1. Synthesis of compound 4 Compound 4 was synthesized by the addition of malonic ester (10 g,62.5 mmol) in the solution of sodium hydride (6 g, 250 mmol) in 100 mLof dry THF. The malonic ester was added dropwise to the solutionmaintaining the 0 C temperature. The solution was stirred for the next30 min and followed by the addition of propargyl bromide (16.36 g,137.5 mmol). Then it was stirred for the next 36 h at room temperature.The crude mixture was washed with water and ethyl acetate twice andfinally, the organic layer was collected. After drying under reducedvacuum a yellow liquid was obtained which was further purified bycolumn chromatography with 95:5 (hexane:ethyl acetate) eluent. Thecompound was kept in freezer to solidify and then the solid was dissolvedin the minimum amount of hexane and again kept in a freeze forthe crystallization. After precipitation, crystals were obtained as thefinal product with a yield of 90%.
85% With potassium carbonate In acetone; toluene for 48h; Heating;
85% With aluminum oxide; sodium ethanolate at 20℃; for 2.5h;
84% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil at -10℃; for 0.25h; Stage #2: propargyl bromide In tetrahydrofuran; toluene; mineral oil at -10 - 25℃; for 20h; 7.1 Step 1: Synthesis of diethyl 2,2-di(prop-2-yn-l-yl)malonate. To a suspension of sodium hydride (60% wt in mineral oil, 4.22 g, 105.5 mmol) in dry THF (100 mL) stirring at -10 °C, dimethyl malonate (6.0 mL, 52.5 mmol) was added dropwise over 10 min. The reaction mixture was stirred at -10 °C for 5 min, and then propargyl bromide (80% wt. in toluene, 12.0 mL, 107.7 mmol) was added dropwise. The reaction mixture was warmed to 25 °C and stirred for 20 h. The reaction mixture was then poured into H2O (50 mL) and Et20 (50 mL), and the layers were separated. The aq layer was extracted with Et20 (3 x 50 mL). The combined organic phases were washed with brine (50 mL), dried over MgSCri, filtered, and concentrated on a rotary evaporator leaving a white solid. The solid was recrystallized from ethyl acetate and hexanes resulting in 9.44 g of a crystalline white solid (84% yield).
84% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; mineral oil at -10℃; for 0.25h; Stage #2: propargyl bromide In tetrahydrofuran; toluene; mineral oil at 25℃; for 20h; 22.1 Step 1: Synthesis of diethyl 2,2-di(prop-2-yn-1-yl)malonate. To a suspension of sodium hydride (60% wt in mineral oil, 4.22 g, 105.5 mmol) in dry THF (100 mL) stirring at -10 °C, dimethyl malonate (6.0 mL, 52.5 mmol) was added dropwise over 10 min. The reaction mixture was stirred at -10 °C for 5 min, and then propargyl bromide (80% wt. in toluene, 12.0 mL, 107.7 mmol) was added dropwise. The reaction mixture was warmed to 25 °C and stirred for 20 h. The reaction mixture was then poured into H2O (50 mL) and Et2O (50 mL), and the layers were separated. The aq layer was extracted with Et2O (3 × 50 mL). The combined organic phases were washed with brine (50 mL), dried over MgSO4, filtered, and concentrated on a rotary evaporator leaving a white solid. The solid was recrystallized from ethyl acetate and hexanes resulting in 9.44 g of a crystalline white solid (84% yield).
68% Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Autoclave; Stage #2: propargyl bromide In tetrahydrofuran for 3h; Inert atmosphere; Autoclave; Reflux;
44.8% Stage #1: diethyl malonate With sodium ethanolate In ethanol for 0.5h; Stage #2: propargyl bromide In ethanol at 60℃; Reflux; 6.a Example 6 - Dipropargyl sugar synthesis and production of AE-ligand a. Synthesis of diethyl diproparglymalonateDiethylmalonate (122.5g, 0.7648 mol) was added to absolute ethanol (800ml) containing sodium ethoxide (prepared from sodium metal, 38.5 g, 1.67mol). After 30 min, propargyl bromide (20Og, 1.68 mol) was slowly added to the stirred suspension, keeping the temperature under 60 C. The mixture was refluxed overnight (15 hours). The precipitated salts were removed by filtration and washed with ethanol. Solvent was removed in vacuo, and the residue diluted with water and extracted with ethanol (2x 200ml). The combined extracts were dried over MgSO4, filtered, washed with Et2O and the solvent removed in vacuo to afford a golden colored oil. The oil was placed on high vacuum (40 C) for 3 hours and allowed to stand. Solids began to crystallize forming an oily solid. Let stand overnight (16 hours). Cyclohexane was charged to flask, solids broken-up, filtered, and washed with cyclohexane to afford white crystalline product (81 gm, 44.8% yield). Reaction was followed by GC.
With ethanol; sodium ethanolate
With potassium carbonate
With sodium ethanolate 1) EtOH, RT, 30 min, 2) 2h, reflux; Yield given. Multistep reaction;
With sodium hydride In tetrahydrofuran
With sodium hydride In tetrahydrofuran at 20℃; Inert atmosphere;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 Embodiment 1 (1) in order to 830mmol sodium hydride as catalyst, will 200mmol malonic acid b diethlyl and 440mmol alkyne-propyl bromide is added to the 250 ml anhydrous acetonitrile in ice-water bath, stirring for 8 hours, product washing with water, extraction with ethyl acetate, decompression turns on lathe does, the volume ratio of 1:100 ethyl acetate: petroleum ether column chromatography separation, to obtain white solid product, i.e. compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; (1) In 820mmol of sodium hydride as catalyst, 200mmol of diethyl malonate 440mmol propargyl bromide was added to 250mL of anhydrous acetonitrile ice-water bath, the reaction was stirred for 8 hours, the product was washed with water, added with ethyl acetate, Save spin dry pressure, volume ratio 1: 100 ethyl acetate: petroleum ether column chromatography to give a white solid product, i.e. compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 2.a.1 Diethyl malonate (200 mmol) and propargyl bromide (440 mmol) were added to anhydrous acetonitrile under ice-cooling with sodium hydride (400 mmol) as a catalyst for 8 hours. The reaction product was washed with water, Ethyl acetate: petroleum ether = 1: 100) to give a white solid product in which the molar ratio of diethyl malonate to propargyl bromide was 1: 2.2;
With potassium carbonate In toluene; acetonitrile for 24h; Glovebox;
Stage #1: diethyl malonate With sodium hydride In tetrahydrofuran; toluene at 0 - 20℃; for 2h; Schlenk technique; Stage #2: propargyl bromide In tetrahydrofuran; toluene at 0 - 20℃;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 2.1 (1) Using 830 mmol of sodium hydride as a catalyst,200 mmol of diethyl malonate was added to 440 mmol of propargyl bromide in 210 mL of anhydrous acetonitrile in an ice-water bath,Stirring reaction for 8 hours, the product was washed with water, extracted with ethyl acetate, dried under reduced pressure,To give the product as a brown solid, i.e., compound 1b
With sodium hydride In acetonitrile; mineral oil for 8h; Cooling with ice;
With sodium hydride In tetrahydrofuran at 25℃; for 12h;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 1) 830 mmol of sodium hydride as catalyst, 200 mmol of diethyl oxalate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice-water bath and the reaction was stirred for 8 hours. The product was washed with water, extracted with ethyl acetate and then dried under reduced pressure. Column chromatography (ethyl acetate: petroleum ether = 1: 70 in volume) gave the product as a white solid, Compound 1.
With sodium hydride In acetonitrile for 5h; Cooling with ice; 2 Example 2 960mmol sodium hydride as catalyst, 200mmol diethyl malonate and 600mmol propargyl bromide was added to 140mL of anhydrous acetonitrile in ice water bath, the reaction was stirred for 5 hours, the product was washed with water, extracted with ethyl acetate and subtracted Press-dry to give a yellow-brown solid product, Compound a-2;
With sodium hydride In acetonitrile at 0℃; for 8h; 1.1 A method for preparing a dihydronaphthalenone derivative containing a spiro ring structure, which comprises the following steps: (1) Using 830 mmol of sodium hydride as a catalyst, 200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to an ice water bath of 210 mL of anhydrous acetonitrile. The reaction was stirred for 8 hours. The product was washedwith water, extracted with ethyl acetate, and dried under reduced pressure. A white solid product, compound a;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 2.1 (1) 830mmol of sodium hydrogen catalyst,200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice water bath.Stir the reaction for 8 hours,The product is washed with water,Extract with ethyl acetate,Drying under reduced pressure,A brownish yellow solid product is obtained,That is compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 (1) using 830 mmol of sodium hydride as a catalyst,200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice water bath.Stir the reaction for 8 hours,The product was washed with water, extracted with EtOAc EtOAc.Obtaining a brownish yellow solid product, compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 2.1 (1) Using sodium hydride 830 mmol as a catalyst, 200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice water bath, and the reaction was stirred for 8 hours. The product was washed with water and extracted with ethyl acetate. Drying under reduced pressure to give a brown-yellow solid product, compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 (1) Using 830mmol of sodium hydride as a catalyst, 200mmol diethyl malonate and 440mmol propargyl bromide added into 210mL anhydrous acetonitrile in ice water bath, the reaction was stirred for 8 hours and the product was washed with water, extracted with ethyl acetate and dried under reduced pressure, and obtained compound 1
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 (1)Using 830 mmol of sodium hydride as a catalyst,200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice water bath, and the reaction was stirred for 8 hours.The product is washed with water,Extracted with ethyl acetate and dried under reduced pressureTo get the product,That is, compound 1;
With sodium hydride In acetonitrile for 8h; Cooling with ice; 1.1 using 830 mmol of sodium hydride as a catalyst,200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile in an ice water bath.The reaction was stirred for 8 hr.Obtained the product, compound 1
With sodium hydride In acetonitrile for 8.5h; Cooling with ice; 3.1 (1) using 830 mmol of sodium hydride as a catalyst,200mmol diethyl malonate and 440mmolPropargyl bromideIn 210 mL of anhydrous acetonitrile,Stir the reaction in an ice water bath for 8.5 hours.The product is washed with water,Extracted with ethyl acetate,Dry under reduced pressure,In a volume ratio of ethyl acetate:Column chromatography with petroleum ether = 1:90 as eluent.After concentration and drying under reduced pressure,Obtaining the white solid product compound a-3;
With sodium hydride In acetonitrile for 8.5h; Cooling with ice; 2.1 The preparation method of the above isoquinolinium ether comprises the following steps: 1) using 830 mmol of sodium hydride as a base,200mmol of diethyl malonate and440mmol of propargyl bromide was added toIn an ice water bath of 210 mL of anhydrous acetonitrile, the reaction was stirred for 8.5 hours, and the product was washed with water.Extract with ethyl acetate, spin dry under reduced pressure, column chromatography (volume ratio ethyl acetate:Petroleum ether = 1:80) to give the product as a white solid.That is, compound 1;
With sodium hydride In acetonitrile for 8.5h; Cooling with ice; 2.1 The method of preparing the exocyclic double bond-containing quinoline derivatives comprising the steps of: (1) Using 830 mmol of sodium hydride as a base, 200 mmol of diethyl malonate and 440 mmol of propargyl bromide were added to anhydrous acetonitrile in an ice water bath, and the reaction was stirred for 8.5 hours. The product was washed with water and extracted with ethyl acetate. Rotary evaporation under reduced pressure to a volume ratio of ethyl acetate: petroleum ether = 1: 80 is a column chromatography eluent,After concentration and drying under reduced pressure, a white solid product is obtained, that is, compound 1b
With sodium hydride In acetonitrile at 0℃; for 8h; 1.1 A preparation method of a triaryl-containing phosphorus oxo ligand, the preparation method includes the following steps: (1) Using 830 mmol of sodium hydride as a catalyst, 200 mmol of diethyl malonate and440 mmol propargyl bromide was added to 210 mL of anhydrous acetonitrile in an ice water bath,The reaction was stirred for 8 hours. The product was washed with water and extracted with ethyl acetate.Spin dry under reduced pressure,A white solid product was obtained, namely compound a-1;
With sodium hydride In acetonitrile at 0℃;
With sodium hydride In acetonitrile for 8.5h; Cooling with ice; 1.1 1) Add 830mmol of sodium hydride, 200mmol of diethyl malonate and 440mmol of propargyl bromide to 210ml of anhydrous acetonitrile in an ice water bath, and stir and react for 8.5 hours. The product is washed with water, Extract with ethyl acetate, Rotate to dry under reduced pressure (using a rotary evaporator to spin off the solvent, add silica gel powder to obtain a solid powder containing drugs), Perform column chromatography with the volume ratio of ethyl acetate: petroleum ether=1:80 as the eluent, Obtain the product, after concentrating and drying under reduced pressure (using a double-row tube to drain the solvent and water that may exist in the product), Namely compound 1a, structural formula:
With sodium hydride In acetonitrile at 0℃;
With sodium hydride In acetonitrile for 8.5h; Cooling with ice; 2.1 A method for synthesizing a benzoxazolidine derivative, the synthesis method is: 1) Using 830mmol sodium hydride as the base, add 200mmol of diethyl malonate and 440mmol of propargyl bromide to 210ml of anhydrous acetonitrile in an ice-water bath, stir and react for 8.5 hours, wash the product with water, extract with ethyl acetate, and reduce pressure Rotate to dryness, column chromatography (volume ratio ethyl acetate: petroleum ether = 1:80) to obtain a white solid product, namely compound 1;
With sodium hydride In acetonitrile at 0℃; Preparation of diyne substrate General procedure: 10 g NaH (60%) and 200-300 mL acetonitrile were added in 500 mL three-necked flask with magnetic stirring. 100 mmol malonate and 30 g 3-bromopropyne (98%) were added in the above 500 mL three-necked flask dropwise in turn by separatory funnel, magnetically stirred for 8-10 h under ice-water bath. The organic phase was extracted with ethyl acetate and dried with anhydrous MgSO4. The solvent was evaporated in vacuo and diyne substrate as white solid were obtained finally.

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[44]Current Patent Assignee: ANHUI NORMAL UNIVERSITY - CN113045586, 2021, A Location in patent: Paragraph 0041; 0052-0054
[45]Yang, Feihu; Zheng, Xiaojie; Lei, Yu; Hu, Qiong; Zhu, Wenjing; Hu, Yimin [Synthesis, 2022, vol. 54, # 4, p. 1125 - 1133]
  • 5
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • [ 29681-57-0 ]
  • diethyl 5-(tert-butyldimethylsiloxy)-1,3-dihydro-6-hydroxy-2H-indene-2,2-dicarboxylate [ No CAS ]
  • 6
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • [ 29681-57-0 ]
  • diethyl 5,6-bis(tert-butyldimethylsiloxy)-1,3-dihydro-2H-indene-2,2-dicarboxylate [ No CAS ]
  • 7
  • [ 2689-88-5 ]
  • [ 153953-34-5 ]
YieldReaction ConditionsOperation in experiment
97% With lithium aluminium tetrahydride In tetrahydrofuran at -6℃; Inert atmosphere;
84% With lithium aluminium tetrahydride In diethyl ether for 12h;
60% With lithium aluminium tetrahydride In diethyl ether at 0 - 20℃; for 36h;
With lithium aluminium tetrahydride
With lithium aluminium tetrahydride In diethyl ether at 20℃; Inert atmosphere;
With lithium aluminium tetrahydride In tetrahydrofuran at 25℃; for 12h;

  • 8
  • [ 2689-88-5 ]
  • [ 107-19-7 ]
  • [ 117926-57-5 ]
YieldReaction ConditionsOperation in experiment
96% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 4h;
96% 8 The substituted benzene 6ae was obtained from the compound 3a and compound 4e in a similar manner as in Example 4 except for the use of the compound 4e (3 mmol) (yield: 96%).1H-NMR (600 MHz, CDCl3): δ 7.20 (s, 1H, Ar), 7.17 (d, 1H, J=8.4 Hz, Ar), 7.14 (d, 1H, J=8.4 Hz, Ar), 4.62 (s, 2H, ArCH2OH), 4.20 (q, 4H, J=6.6 Hz, OCH2CH3), 3.57 (s, 4H, ArCH2C), 1.25 (t, 6H, J=6.6 Hz, OCH2CH3).13C-NMR (150 MHz, CDCl3): δ 171.6, 140.4, 139.8, 139.5, 125.9, 124.2, 123.0, 65.3, 61.7, 60.5, 40.3, 40.1, 14.0.IR (neat): 3550, 2984, 2938, 1753, 1735, 1727, 1712, 1258, 1186, 1157 cm-1.Anal. Calcd for C16H20O5: C, 65.74; H, 6.90. Found: C, 65.40; H, 6.95.
77% With (R)-(+)-N-benzyl-N-diphenylphosphino-2-methyl-2-propanesulfinamide; bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In 1,2-dichloro-ethane for 2h; Inert atmosphere; Reflux;
64% In ethanol at 25℃; for 1.5h;
52% In tetrahydrofuran for 17h; Ambient temperature; other alkynols;
52% In tetrahydrofuran for 17h; Ambient temperature;

  • 9
  • [ 106-96-7 ]
  • [ 105-53-3 ]
  • [ 17920-23-9 ]
  • [ 2689-88-5 ]
YieldReaction ConditionsOperation in experiment
47% Stage #1: diethyl malonate With sodium ethanolate In ethanol for 1h; Stage #2: propargyl bromide In ethanol; toluene at 0 - 20℃; for 21h;
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In water for 2.5h;
  • 10
  • [ 2689-88-5 ]
  • [ 2028-63-9 ]
  • [ 131389-07-6 ]
YieldReaction ConditionsOperation in experiment
81% With cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 40℃; Inert atmosphere;
8% In tetrahydrofuran for 17h; Ambient temperature;
  • 11
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • [ 29681-57-0 ]
  • 4-(tert-Butyl-dimethyl-silanyl)-5-oxo-3,4,5,6-tetrahydro-1H-pentalene-2,2-dicarboxylic acid diethyl ester [ No CAS ]
  • 12
  • [ 2689-88-5 ]
  • [ 65881-41-6 ]
  • Diethyl 5-(N-acetylaminomethyl)indane-2,2-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
40% With n-butyllithium In tetrahydrofuran Ambient temperature;
  • 13
  • [ 2689-88-5 ]
  • [ 29681-57-0 ]
  • 1,2-bis[(tert-butyldimethylsilyl)methyl]-4,4-di(ethoxycarbonyl)-cyclopent-1-ene [ No CAS ]
  • 14
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • [ 254752-58-4 ]
YieldReaction ConditionsOperation in experiment
85% In dichloromethane at 100℃; for 48h;
  • 15
  • [ 2689-88-5 ]
  • 1,3-dihydro-6-methyl-5-isobenzofuran-5-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% In tetrahydrofuran at 70℃; for 65h;
  • 16
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • [ 536-74-3 ]
  • 5-oxo-6,8-diphenyl-5,5a-dihydro-3<i>H</i>-cyclopenta[<i>c</i>]indene-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With dicobalt octacarbonyl In dichloromethane at 130℃; for 18h;
  • 17
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • C27H32O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With cyclopenta-1,3-diene In dichloromethane at 110℃; for 18h;
  • 18
  • [ 2689-88-5 ]
  • [ 85110-26-5 ]
  • [ 528570-72-1 ]
YieldReaction ConditionsOperation in experiment
81% With triphenylphosphine In acetonitrile at 20℃; for 24h;
35% In acetonitrile at 60℃; for 72h;
  • 19
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • 7,7-bis (ethoxycarbonyl)-bicyclo [3.3.0] octa-1,5-dien-3-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With potassium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 70℃; for 8h;
  • 20
  • [ 2689-88-5 ]
  • [ 201230-82-2 ]
  • C27H32O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% In tetrahydrofuran at 150℃; for 18h;
  • 21
  • [ 2689-88-5 ]
  • [ 18752-21-1 ]
  • 3-((E)-3-Triphenylsilanyl-propenyl)-4-vinyl-cyclopent-3-ene-1,1-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% In dichloromethane at 20℃; for 12h;
  • 22
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 90 percent of 5-membered rings by NMR, Mn 62700 Da and Mw/Mn 3.68 by GPC, Mn 45400 Da and Mw/Mn 3.67 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 23
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 83 percent of 5-membered rings by NMR, Mn 133000 Da and Mw/Mn 3.38 by GPC, Mn 132000 Da and Mw/Mn 3.50 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 24
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 88 percent of 5-membered rings by NMR, Mn 98600 Da and Mw/Mn 2.78 by GPC, Mn 87000 Da and Mw/Mn 2.41 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 25
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 89 percent of 5-membered rings by NMR, Mn 112000 Da and Mw/Mn 2.61 by GPC, Mn 93200 Da and Mw/Mn 2.33 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 26
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 86 percent of 5-membered rings by NMR, Mn 133000 Da and Mw/Mn 1.88 by GPC, Mn 99600 Da and Mw/Mn 2.08 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 27
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 88 percent of 5-membered rings by NMR, Mn 117000 Da and Mw/Mn 1.79 by GPC, Mn 94500 Da and Mw/Mn 1.80 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 28
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 85 percent of 5-membered rings by NMR, Mn 120000 Da and Mw/Mn 1.96 by GPC, Mn 96000 Da and Mw/Mn 1.98 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃;
  • 29
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with > 95 percent of 5-membered rings by NMR, Mn 20300 Da and Mw/Mn 1.68 by GPC, Mn 17700 Da and Mw/Mn 1.23 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane at 20℃; for 12h;
  • 30
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 89 percent of 5-membered rings by NMR, Mn 134000 Da and Mw/Mn 3.05 by GPC, Mn 131000 Da and Mw/Mn 3.18 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane at 20℃;
  • 31
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with 6- and 81 percent of 5-membered rings by NMR, Mn 141000 Da and Mw/Mn 2.69 by GPC, Mn 92400 Da and Mw/Mn 3.72 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane at 20℃;
  • 32
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, with > 95 percent of 5-membered rings by NMR, Mn 19600 Da and Mw/Mn 1.75 by GPC, Mn 13000 Da and Mw/Mn 1.94 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane at 20℃; for 12h;
  • 33
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 13700 Da and Mw/Mn 1.46 by GPC, Mn 8200 Da and Mw/Mn 1.25 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane
  • 34
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 22800 Da and Mw/Mn 1.88 by GPC, Mn 21400 Da and Mw/Mn 1.75 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane
  • 35
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 26000 Da and Mw/Mn 1.72 by GPC, Mn 25000 Da and Mw/Mn 1.58 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane
  • 36
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 28200 Da and Mw/Mn 1.96 by GPC, Mn 29000 Da and Mw/Mn 1.95 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With ethanol; tetra-n-butyltin(IV); molybdenum(V) chloride In dichloromethane
  • 37
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 15600 Da and Mw/Mn 1.61 by GPC, Mn 6770 Da and Mw/Mn 1.65 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane
  • 38
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 21500 Da and Mw/Mn 1.60 by GPC, Mn 20000 Da and Mw/Mn 1.13 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane
  • 39
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 26900 Da and Mw/Mn 2.03 by GPC, Mn 22600 Da and Mw/Mn 1.33 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane
  • 40
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), product of cyclopolymerization, Mn 28200 Da and Mw/Mn 2.24 by GPC, Mn 25300 Da and Mw/Mn 1.90 by light scattering; monomer(s): diethyl dipropargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With ethanol; tetra-n-butyltin(IV); molybdenum(VI) tetrachloride oxide In dichloromethane
  • 41
  • [ 2689-88-5 ]
  • [ 762-72-1 ]
  • 3-((E)-3-Trimethylsilanyl-propenyl)-4-vinyl-cyclopent-3-ene-1,1-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% In dichloromethane at 20℃; for 12h;
  • 42
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), Mw: 15,500, Mn: 11,100, PDI: 1.4; monomer(s): diethyl propargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% In chloroform at 20℃; for 3h;
  • 43
  • [ 2689-88-5 ]
  • poly(diethyl dipropargylmalonate), Mw: 16,400, Mn: 11,700, PDI: 1.4; monomer(s): diethyl propargylmalonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% In chloroform at 40℃; for 3h;
  • 44
  • [ 110-65-6 ]
  • [ 2689-88-5 ]
  • [ 131389-15-6 ]
YieldReaction ConditionsOperation in experiment
83% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 8h;
72% With (R)-(+)-N-benzyl-N-diphenylphosphino-2-methyl-2-propanesulfinamide; bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In 1,2-dichloro-ethane for 7h; Inert atmosphere; Reflux;
68% With titanium(IV) isopropylate; Wilkinson's catalyst In ethanol for 12h; Inert atmosphere; Reflux; 4.4. Preparation of compound 3a The solution of compound 2a (1.7 g, 7.2 mmol), and 2-butyne-1,4-diol (1.85 g, 21.60 mmol) in dry ethanol (35 mL) was degassed with nitrogen for 15 min. Later, Wilkinson’s catalyst (166 mg, 2.5 mol %) and Ti(OiPr)4 (511 mg, 25 mol %) were added and the reaction mixture was refluxed for 12 h. At the conclusion of the reaction (TLC monitoring), the solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography (20% EtOAc-petroleum ether) to deliver compound 3a (2.14 g, 68%) as a white solid. The 1H and 13C spectra matched with the literature reported spectral data.
  • 45
  • [ 2689-88-5 ]
  • [ 1002-36-4 ]
  • 5-butyl-6-hydroxymethyl-indan-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 12h;
  • 46
  • [ 2689-88-5 ]
  • [ 16930-95-3 ]
  • 6-butyl-indan-2,2,5-tricarboxylic acid triethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 8h;
  • 47
  • [ 2689-88-5 ]
  • [ 22174-59-0 ]
  • 5-methoxymethyl-6-phenyl-indan-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 8h;
  • 48
  • [ 2689-88-5 ]
  • [ 5272-36-6 ]
  • 5-hydroxymethyl-6-trimethylsilanyl-indan-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 12h;
  • 49
  • [ 2689-88-5 ]
  • [ 1504-58-1 ]
  • 5-hydroxymethyl-6-phenyl-indan-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 4h;
  • 50
  • [ 2689-88-5 ]
  • [ 1165-53-3 ]
YieldReaction ConditionsOperation in experiment
91% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃;
  • 51
  • [ 2689-88-5 ]
  • [ 536-74-3 ]
  • 2,2-diethyl 5-phenyl-2,3-dihydro-1H-indene-2,2-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran; water at 25℃; for 4h;
92% at 20℃; for 0.5h; 87 The substituted benzene 6ab was obtained from the compound 3a and compound 4b in a similar manner as in Example 83 except for stirring at room temperature for 30 minutes (yield: 92%).
92% With di-bromo-bis(tricyclohexylphosphine)-cobalt(II); [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 3h; Inert atmosphere; Glovebox; Photolysis;
88% With palladium-gold alloy nanoparticles supported on TiO2 catalyst In toluene at 100℃; Schlenk technique; Inert atmosphere;
87% With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; N,N-dimethyl-formamide In toluene for 24h; Inert atmosphere; Reflux;
87% With dibromo-bis-triphenylphosphine cobalt; N-ethyl-N,N-diisopropylamine In 1,2-dichloro-ethane at 35℃; for 3h; Irradiation;
85% With dicobalt octacarbonyl In toluene at 200℃; Flow reactor;
81% With rhodium(III) chloride; N-ethyl-N,N-diisopropylamine In isopropyl alcohol for 2h; Heating;
80% With Au-Pd/TiO2 In toluene at 75℃; for 2h; Inert atmosphere; 23 Example 23 General procedure: 0.3 mmol of alkynes 9 (reaction was carried out for each of 5 types 9a to 9e) described in the following chemical formula and alkynes 1 were dissolved in 1 ml of toluene, and the solution was adjusted to 6 mol% in total solution The catalyst of Example 1 was added and reacted at 75 ° C. under an argon atmosphere for each compound for the time period shown below to give a benzene compound represented by Compound 10 (wherein R corresponds to each of R 9a to 9e) .
71% With (R)-(+)-N-benzyl-N-diphenylphosphino-2-methyl-2-propanesulfinamide; bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; hydrogen In 1,2-dichloro-ethane at 20℃; for 6h; Inert atmosphere;
50% In toluene for 0.0333333h; microwave irradiation;
With styrene; cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 20℃; Inert atmosphere;

Reference: [1]Saino, Naoko; Amemiya, Fumihiro; Tanabe, Emi; Kase, Kouki; Okamoto, Sentaro [Organic Letters, 2006, vol. 8, # 7, p. 1439 - 1442]
[2]Current Patent Assignee: NISSAN CHEMICAL CORPORATION - US2010/168441, 2010, A1 Location in patent: Page/Page column 35-36
[3]Ruhl, Kyle E.; Rovis, Tomislav [Journal of the American Chemical Society, 2016, vol. 138, # 48, p. 15527 - 15530]
[4]Miura, Hiroki; Tanaka, Yumi; Nakahara, Karin; Hachiya, Yuka; Endo, Keisuke; Shishido, Tetsuya [Angewandte Chemie - International Edition, 2018, vol. 57, # 21, p. 6136 - 6140][Angew. Chem., 2018, vol. 130, p. 6244 - 6248,5]
[5]Location in patent: experimental part Mallagaray, Alvaro; Mohammadiannejad-Abbasabadi, Kazem; Medina, Sandra; Dominguez, Gema; Perez-Castells, Javier [Organic and Biomolecular Chemistry, 2012, vol. 10, # 33, p. 6665 - 6672]
[6]Ravetz, Benjamin D.; Wang, Jason Y.; Ruhl, Kyle E.; Rovis, Tomislav [ACS Catalysis, 2019, vol. 9, # 1, p. 200 - 204]
[7]García-Lacuna, Jorge; Domínguez, Gema; Blanco-Urgoiti, Jaime; Pérez-Castells, Javier [Organic Letters, 2018, vol. 20, # 17, p. 5219 - 5223]
[8]Yoshida, Kenta; Morimoto, Ichiro; Mitsudo, Koichi; Tanaka, Hideo [Chemistry Letters, 2007, vol. 36, # 8, p. 998 - 999]
[9]Current Patent Assignee: TOKYO METROPOLITAN UNIVERSITY - JP2019/1757, 2019, A Location in patent: Paragraph 0034
[10]Location in patent: experimental part Brun, Sandra; Parera, Magda; Pla-Quintana, Anna; Roglans, Anna; León, Thierry; Achard, Thierry; Sol, Jordi; Verdaguer, Xavier; Riera, Antoni [Tetrahedron, 2010, vol. 66, # 46, p. 9032 - 9040]
[11]Teske, Jesse A.; Deiters, Alexander [Journal of Organic Chemistry, 2008, vol. 73, # 1, p. 342 - 345]
[12]Location in patent: experimental part Watanabe, Jun-Ichi; Sugiyama, Yu-Ki; Nomura, Ayami; Azumatei, Suzumi; Goswami, Avijit; Saino, Naoko; Okamoto, Sentaro [Macromolecules, 2010, vol. 43, # 5, p. 2213 - 2218]
  • 52
  • [ 2689-88-5 ]
  • [ 768-60-5 ]
  • 5-(4-methoxy-phenyl)-indan-2,2-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; cobalt(II) chloride; zinc In tetrahydrofuran at 25℃; for 4h;
  • 53
  • (2R,3S)-5-ethynyl-2-(((4-methylbenzoyl)oxy)methyl)tetrahydrofuran-3-yl 4-methylbenzoate [ No CAS ]
  • [ 2689-88-5 ]
  • 1-[2,2-bis(ethoxycarbonyl)-1,3-dihydro-2H-inden-5-yl]-1,2-dideoxy-3,5-di-O-(4-toluoyl)-D-ribofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With RhCl(PPh3)3 In toluene at 20℃; for 48h;
  • 54
  • [ 890025-16-8 ]
  • [ 2689-88-5 ]
  • 1β-[2,2-bis(ethoxycarbonyl)-1,3-dihydro-2H-inden-5-yl]-1,2-dideoxy-3,5-di-O-(4-toluoyl)-D-ribofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With RhCl(PPh3)3 In toluene at 20℃; for 48h;
  • 55
  • [ 916346-26-4 ]
  • [ 2689-88-5 ]
  • 6-[6-butyl-2,2-di(carboxyethyl)indan-5-yl]-9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-9H-purine [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With triphenylphosphine In acetonitrile at 20℃; for 24h;
  • 56
  • [ 2689-88-5 ]
  • [ 91077-92-8 ]
  • 6-[6-trimethylsilyl-2,2-di(carboxyethyl)indan-5-yl]-9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-9H-purine [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With triphenylphosphine In acetonitrile at 20℃; for 48h;
  • 57
  • [ 2689-88-5 ]
  • [ 78-82-0 ]
  • 3-isopropyl-5,7-dihydro-[2]pyrindine-6,6-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With 1,2-bis-(diphenylphosphino)ethane; cobalt(II) chloride; zinc In 1-methyl-pyrrolidin-2-one at 25℃; for 1h;
  • 58
  • [ 2689-88-5 ]
  • [ 109-78-4 ]
  • 3-(2-hydroxy-ethyl)-5,7-dihydro-[2]pyrindine-6,6-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With 1,2-bis-(diphenylphosphino)ethane; cobalt(II) chloride; zinc In 1-methyl-pyrrolidin-2-one at 25℃; for 2h;
  • 59
  • [ 2689-88-5 ]
  • [ 75-05-8 ]
  • 3-methyl-5,7-dihydro-[2]pyrindine-6,6-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With 1,2-bis-(diphenylphosphino)ethane; cobalt(II) chloride; zinc In 1-methyl-pyrrolidin-2-one at 25℃; for 1h;
100 %Spectr. With cobalt(II) chloride hexahydrate; 1,2-bis-(diphenylphosphino)ethane; zinc at 50℃;
  • 60
  • [ 2689-88-5 ]
  • [ 107-12-0 ]
  • 3-ethyl-5,7-dihydro-[2]pyrindine-6,6-dicarboxylic acid diethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With 1,2-bis-(diphenylphosphino)ethane; cobalt(II) chloride; zinc In 1-methyl-pyrrolidin-2-one at 25℃; for 1h;
  • 61
  • [ 2689-88-5 ]
  • [ 693-02-7 ]
  • diethyl 5-butyl-1,3-dihydro-2H-indene-2,2-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With dicobalt octacarbonyl In toluene at 200℃; Flow reactor;
78% In toluene at 82℃; for 0.0333333h; microwave irradiation;
70% With bis(triphenylphosphine)nickel(0) dicarbonyl In toluene at 82℃; Inert atmosphere; Microwave irradiation;
63% 5 The substituted benzene 6aa was obtained from the compound 3a and compound 4a in a similar manner as in Example 4 except for the use of the compound 4a (3 mmol) (yield: 63%).1H-NMR (600 MHz, CDCl3): δ 7.08 (d, 1H, J=7.8 Hz, Ar), 7.01 (s, 1H, Ar), 6.97 (d, 1H, J=7.8 Hz, Ar), 4.20 (q, 4H, J=7.2 Hz, OCH2CH3), 3.56 (s, 2H, ArCH2C), 3.55 (s, 2H, ArCH2C), 2.56 (t, 2H, J=7.8 Hz, ArCHhd 2CH2), 1.56 (quint, 2H, J=7.8 Hz, CH2CH2CH3), 1.34 (sext, 2H, J=7.8 Hz, CH2CH2CH3), 1.25 (t, 6H, J=7.2 Hz, OCH2CH3), 0.91 (t, 3H, J=7.8 Hz, CH2CH2CH3).13C-NMR (150 MHz, CDCl3): δ 171.8, 141.7, 140.0, 137.1, 127.1, 124.1, 123.8, 61.6, 60.6, 40.4, 40.1 35.5, 33.8, 22.4, 14.0, 13.9.IR (neat): 2980, 2959, 2932, 2859, 1738, 1725, 1248, 1184, 1157 cm-1.Anal. Calcd for C19H26O4: C, 71.67; H, 8.23. Found: C, 71.77; H, 8.34.

  • 62
  • [ 2689-88-5 ]
  • [ 910311-13-6 ]
YieldReaction ConditionsOperation in experiment
88% With methanesulfonic acid; dichloro( 1,5-cyclooctadiene)platinum(ll); water In methanol at 70℃; for 3h; Inert atmosphere; Sealed reactor;
87% With methanesulfonic acid; water In methanol at 70℃; for 1h;
82% With methanesulfonic acid; AgNO<SUB>3</SUB>(PPh<SUB>3</SUB>); water In methanol at 70℃; for 3h; Ionic liquid; Inert atmosphere;
78% With trifluorormethanesulfonic acid; water; mercury dichloride In methanol at 70℃; for 3h; Inert atmosphere;

  • 63
  • [ 2689-88-5 ]
  • [ 932-87-6 ]
  • [ 1068614-43-6 ]
YieldReaction ConditionsOperation in experiment
77% Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With copper(l) iodide; P-olefin; triethylamine; bis(dibenzylideneacetone)-palladium(0) In N,N-dimethyl-formamide for 0.0833333h; Inert atmosphere; Stage #2: 1-Bromo-2-phenylacetylene In N,N-dimethyl-formamide at 20℃; for 9h; Inert atmosphere;
  • 64
  • [ 2689-88-5 ]
  • [ 932-87-6 ]
  • [ 1068614-44-7 ]
YieldReaction ConditionsOperation in experiment
78% Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With copper(l) iodide; P-olefin; triethylamine; bis(dibenzylideneacetone)-palladium(0) In N,N-dimethyl-formamide for 0.0833333h; Inert atmosphere; Stage #2: 1-Bromo-2-phenylacetylene In N,N-dimethyl-formamide at 20℃; for 9h; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran for 12h; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2) the 80mmol compound 1 and 176mmol phenylacetylene mixed in the bromide 2mmolPd (PPh3)2Cl2/CuI in oxygen-free catalytic system, mol ratio Pd (PPh3)2Cl2: CuI=3:1, to 320mmol triethylamine as the alkali, to 200 ml anhydrous acetonitrile as a solvent, stirring reaction at room temperature 12 hours, the product is washed with water, extraction with ethyl acetate, decompression turns on lathe does, the volume ratio of 1:100 ethyl acetate: petroleum ether column chromatography separation, to obtain white solid product, that is, precursor compounds 2.
With copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; (2) The compound 1 were mixed in 80mmol 1.09mmolPd (PPh bromide with phenylacetylene 200mmol3)2Cl2/ CuI in dry oxygen-free catalyst system, the molar ratio of Pd (PPh3)2Cl2: CuI = 3: 1, to 340mmol triethylamine as base to 200ml dry acetonitrile as solvent, the reaction was stirred at room temperature for 12 hours, the product was washed with water, extracted with ethyl acetate, dried under reduced pressure to spin, with a volume ratio of 1: 100 ethyl acetate: petroleum ether column chromatography to give a light brown solid, i.e. compound 2 precursor
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; for 12h; 2.a.2 Synthesis of precursor compounds A white solid product (80 mmol) was mixed with phenylethynyl bromide in Pd (PPh3)2Cl2: CuI (3: 1). The reaction was stirred at room temperature for 12 hours. The reaction product was washed with water and extracted with ethyl acetate. (By volume ethyl acetate: petroleum ether = 1: 100) to give the product as a light brown solid, with a molar ratio of the product as a white solid to phenylethynyl bromide of 1: 2.2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 2.2 (2) 80 mmol of compound 1 was mixed with 200 mmol of phenylethynyl bromide in Pd (PPh3) 2Cl2 / CuI(PPh3) 2Cl2: CuI = 3: 1 in the anhydrous anaerobic catalyzed system (2.56 mmol / 0.85 mmol)The reaction was stirred at room temperature for 12 hours with 336 mmol of triethylamine as a base and 150 mL of anhydrous acetonitrile as a solvent,The product was washed with water, extracted with ethyl acetate, dried under reduced pressure, washed with ethyl acetate in a volume ratio of 1:60:Petroleum ether column chromatography to give the product as a white solid, i.e. precursor compound 2b.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; for 12h; 1.a.2 (2) 80mmol Compound 1 was mixed with 200mmol phenylethynyl bromide in 1.3gPd (PPh3) 2Cl2 / CuI anhydrous anaerobic catalytic system, the molar ratio of Pd (PPh3) 2Cl2 and Cul material is 3: 1, with 320 mmol of triethylamine as base, to 200 mlThe reaction mixture was stirred at room temperature for 12 hours. The product was washed with water, extracted with ethyl acetate and dried under reduced pressure. The residue was purified by column chromatography (ethyl acetate: petroleum ether = 1: 100 by volume) to give a light brown solid product , Ie, precursor compound 2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 2) 80 mmol of compound 1 was mixed with 200 mmol of phenylethynyl bromide in a Pd(PPh3)2Cl2 / CuI anhydrous anaerobic catalytic system at a molar ratio of Pd (PPh 3) 2 Cl 2: Cul = 3: 1. Using 336 mmol of triethylamine as base and 150 mL of anhydrous acetonitrile as solvent, the reaction was stirred at room temperature for 12 hours. The product was washed with water, extracted with ethyl acetate, and then dried under reduced pressure. Column chromatography (ethyl acetate: petroleum ether = 1: 90 by volume) then gave the product as a light brown solid, ie, precursor compound 2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1 Example 1 The present embodiment also provides a method for preparing the above diaryl selenide derivatives:Diacetylene compound bridged with diethyl malonate (20 mmol) and phenylacetylene bromide (48 mmol) were added to a reaction flask, mixed with anhydrous Pd catalyst (PPh3) 2C12 and Cul as catalysts In which the amount of catalyst was 0.8 mmol and Pd (PPh3) 2C12: Cul = 3: 1. The reaction product was stirred at room temperature for 12 hours with triethylamine (50 mmol) as base and anhydrous acetonitrile (40 mL) as solvent. The reaction product was washed with 15% hydrochloric acid solution, 10% sodium bicarbonate solution and saturated brine ; Then extracted with ethyl acetate, dried under reduced pressure and the residue was purified by column chromatography (ethyl acetate to petroleum ether in a volume ratio of 1:40) to give a light brown solid product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1 Example 1 Diethyldiethylether bridged diyneCompound (20 mmol) and phenylacetylene bromide (48 mmol) were added to the reaction flaskin,In the anhydrous oxygen-free catalytic system in which Pd(PPh3)2Cl2 and CuI are used as catalysts,The amount of catalyst was 0.8 mmol and Pd(PPh3)2Cl2:CuI=3:1.Triethylamine (50 mmol) was used as a base and anhydrous acetonitrile (40 mL) was used as a solvent.The reaction was stirred at room temperature for 12 hours and the reaction product was successively treated with a 15% hydrochloric acid solution.10% sodium bicarbonate solution,Saturated brine was washed separately; then extracted with ethyl acetate and evaporated under reduced pressure.Column chromatography (volume ratio of ethyl acetate to petroleum ether in the eluent of 1 : 40) gave a light brown solid product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2) 80 mmol of compound a and 200 mmol of phenylethynyl bromide are mixed in Pd(PPh3)2Cl2/CuI anhydrous oxygen-freecatalytic system (2.56 mmol/0.85 mmol) with a molar ratio Pd(PPh3)2Cl2:CuI=3:1. 336 mmol of triethylamine was used as a base and stirred in anhydrous acetonitrile (150 mL) for 12 hours at 20°C. The product was washed with water, extracted withethyl acetate and water, and then separated by reduced pressure to obtain a volume ratio of 1:40. Ethyl acetate: petroleumether column chromatography gave a yellow-green solid product, compound b.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2) 80 mmol of compound 1 and 200 mmol of phenylethynyl bromide were mixed in an anhydrous anaerobic catalytic system of Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol),Molar ratio Pd(PPh3)2Cl2: CuI=3:1,Using 336 mmol of triethylamine as a base,150mL anhydrous acetonitrile as solventThe reaction was stirred at room temperature for 12 hours.The product was washed with water, extracted with EtOAc EtOAc EtOAc.Obtaining a pale yellow solid product,That is, the product tetrayne.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2) 80mmol of compound 1 was mixed with 200mmol of phenylacetylene bromide in an anhydrous anaerobic catalytic system of Pd (PPh3) 2CI2/CuI (2.56mmol/0.85mmol), molar ratio Pd (PPI13) 2CI2: Cul = 3:1, using 336mmol of triethylamine as a base, 150mL anhydrous acetonitrile as solvent, the reaction was stirred at room temperature for 12 hours, the product is washed with water, extract with ethyl acetate and spin dry under reduced pressure, separation with ethyl acetate: petroleum ether column chromatography at a volume ratio of 1:60, obtained tetrayne
With copper(l) iodide; bis(triphenylphosphine)palladium(II) dichloride; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2)80 mmol of compound 1 and 200 mmolPhenylethynyl bromide mixed in Pd(PPh3)2Cl2/CuIAnhydrous anoxic catalytic system (2.56mmol/0.85mmol),Molar ratio Pd(PPh3)2Cl2: CuI=3:1, with 336 mmol of triethylamine as a base,The reaction was stirred at room temperature for 12 hours with 150 mL of anhydrous acetonitrile as a solvent.The product was washed with water, extracted with EtOAc EtOAcUse ethyl acetate in a volume ratio of 1:60:Separation of petroleum ether column chromatography,Get the product,That is, the precursor compound 2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1 A diyne compound (20 mmol) bridged with diethyl malonate and phenylacetylene bromide (48 mmol) were added to the reaction flask.Mixing Pd(PPh3)2Cl2 and CuI as a catalyst in an anhydrous anaerobic catalytic system, wherein the amount of the catalyst is 0.8 mmol,Pd(PPh3)2Cl2: CuI=3:1. Using triethylamine (50 mmol) as a base,The reaction was stirred at room temperature for 12 hours under anhydrous acetonitrile (40 mL).The reaction product was successively treated with 15% hydrochloric acid solution,Wash with 10% sodium bicarbonate solution and saturated brine; then extract with ethyl acetate, spin dry under reduced pressure, column chromatography (volume ratio of ethyl acetate to petroleum ether in the eluent)The product was obtained as a light brown solid at 1:40.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; Inert atmosphere; 1.2 80 mmol of the compound 1 prepared in the step (1) and 200 mmol of phenylethynyl bromide in an anhydrous anaerobic catalytic system of Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol), molar ratio Pd(PPh3) 2Cl2: CuI=3:1, using 336 mmol of triethylamine as a base, 150 mL of anhydrous acetonitrile as a solvent, stirring at room temperature for 12 hours, the product was washed with water, usingExtracted with ethyl acetate, vortexed under reduced pressure, and separated by ethyl acetate: petroleum ether column chromatography at a volume ratio of 1:60 to obtain product precursor compound 2, which is a tetraacetyl compound.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 11h; 2.2 (2) mixing 80 mmol of compound 1b with 200 mmol of phenylethynyl bromide in an anhydrous anaerobic catalytic system of Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol),The molar ratio of Pd(PPh3)2Cl2: CuI=3:1, using 336 mmol of triethylamine as a base, 150 mL of anhydrous acetonitrile as a solvent, and stirring at room temperature for 11 hours. The product was washed with water and extracted with ethyl acetate. Rotary evaporation under reduced pressure to a volume ratio of ethyl acetate: petroleum ether = 1: 80 as eluant for column chromatography, concentrated to dryness under reduced pressure to give a pale yellow solid product, i.e., the precursor compound 2b
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; for 12h; 1.2 (2) 80 mmol of compound a-1 and200mmol phenylethynyl bromide is mixed in the anhydrous and oxygen-free catalytic system of Pd (PPh3) 2Cl2 / CuI(2.56mmol / 0.85mmol),Molar ratio Pd (PPh3) 2Cl2: CuI = 3: 1, 336 mmol of triethylamine as base,150 mL of anhydrous acetonitrile was used as a solvent, and the reaction was stirred at 0 ° C for 12 hours. The product was washed with water.Extract with ethyl acetate, spin dry under reduced pressure, and use ethyl acetate with a volume ratio of 1:40:Petroleum ether column chromatography gave a white solid product, compound b-1.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 11h; 1.2 2) Mix 80mmol of compound 1a and 200mmol of phenylethynyl bromide in an anhydrous and oxygen-free catalytic system of Pd(PPh3)2Cl2/CuI (2.56mmol/0.85mmol), The molar ratio of Pd(PPh3)2Cl2:CuI=3:1, with 336mmol triethylamine as base, Using 150mL anhydrous acetonitrile as solvent, The reaction was stirred at room temperature for 11 hours, the product was washed with water, Extract with ethyl acetate, spin dry under reduced pressure, Perform column chromatography with the volume ratio of ethyl acetate: petroleum ether=1:80 as the eluent, After concentration and drying under reduced pressure, a light yellow solid product is obtained, namely the precursor compound 2a (tetraacetylene compound), the structural formula is
Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: 1-Bromo-2-phenylacetylene With triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Preparation of tetrayne substrate General procedure: 0.6 g Pd(PPh3)2Cl2, 0.5 g CuI and 40 mmol diyne substrate were added in 500 mL three-necked flask, protected with anhydrous anaerobic conditions under argon. After 0.5 h, 250-300 mL acetonitrile, 16.16 g Et3N and 100 mmol brominated aryl alkyne were added in turn, magnetically stirred for 10-12 h under ice-water bath. The organic phase was extracted with ethyl acetate and dried with anhydrous MgSO4. It was separated by column chromatography on silica gel to obtain tetrayne substrate as white solid finally.

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  • 65
  • [ 2689-88-5 ]
  • [ 57-63-6 ]
  • [ 1184119-79-6 ]
YieldReaction ConditionsOperation in experiment
56% Wilkinson's catalyst; In toluene; acetonitrile; at 20℃; for 48h; Example 1 PN202: 17alpha[2,2-Bis(ethoxycarbonyl)-1,3-dihydro-2H-inden-5-yl]-estradiol 17alpha-Ethynylestradiol (0.25 mmol, 74 mg), diethyl 2,2-(diprop-2-ynyl)-1,3-propandioate (0.3 mmol, 70.8 mg), RhCl(PPh3)3 (0.025 mmol, 23 mg). Column chromatography on silica gel (2/1 hexan/EtOAc) yielded 75 mg (56%) of a colorless compound. M.p. 164 C.; [alpha]D=+35 (c 0.022 g/ml, acetone); 1H NMR (400 MHz, C6D6) delta 0.71-0.79 (m, 1H), 0.87 (t, J=6.8 Hz, 3H), 0.88 (t, J=6.8 Hz, 3H), 1.06 (s, 3H), 1.03-1.12 (m, 1H), 1.29-1.42 (m, 4H), 1.61-1.75 (m, 4H), 1.88-2.00 (m, 2H), 2.18-2.23 (m, 1H), 2.58-2.70 (m, 2H), 3.73-3.85 (m, 4H), 3.91 (q, J=6.8 Hz, 2H), 3.92 (q, J=6.8 Hz, 2H), 5.14 (s, 1H), 6.47 (d, J=2.8 Hz, 1H), 6.57 (dd, J=8, 2.8 Hz, 1H), 6.94 (d, J=8 Hz, 1H), 7.04 (d, J=8 Hz, 1H), 7.164 (s, 1H) signal overlapped, 7.37 (s, 1H); 13C NMR (100 MHz, C6D6) delta 14.60 (2*), 15.74, 25.05, 27.33, 28.46, 30.62, 34.67, 39.63, 40.46, 41.37, 41.76, 44.20, 47.83, 49.15, 61.66, 62.35 (2*), 86.64, 113.73, 116.23, 123.90, 124.49, 127.40, 129.23, 133.05, 138.56, 139.50, 140.19, 146.60, 155.06, 172.47 (2*); IR (ATR ZnSe) nu 3398, 2958, 2927, 2870, 1727, 1711, 1610, 1502, 1442, 1283, 1249, 1185, 1068, 1049, 1008 cm-1; MS (EI) 532 (8), 514 (72), 499 (17), 425 (17), 314 (12), 213 (56), 149 (77); HRMS (EI) calculated for C33H40O6 532.282489. Found 532.283226.
56% Wilkinson's catalyst; In toluene; acetonitrile; at 20℃; for 48h; Examples; The general method for the synthesis of the compounds according to the inventionThe novel compounds according to the invention were prepared by the novel method according to the invention, i.e. by cyclotrimerisation as described above. Particularly, the preferable method was used: RhCI(PPh3)3 (0.05 mmol, 46 mg) and appropriate diyne of general formula III (0.6 mmol) were added to the solution of 17alpha-ethynylestradiol (0.5 mmol, 150 mg) in the mixture of dry toluene (6 ml) and acetonitrile (1 ml). The reaction mixture was stirred at 20 0C for 48 hours or until the starting compounds were completely consumed (as controlled by TLC). The solvents were then evaporated and the residue was treated by chromatography on silica gel. This method produced a colorless compound which was further characterized by 1H and 13C NMR spectroscopy, infra-red spectroscopy and mass spectroscopy.Using this general method and by the use of starting compounds described above following advantageous compounds were prepared: <n="19"/>Example 1PN202: 17alpha-[2,2-Bis(ethoxycarbonyl)-l,3-dihydro-2H-inden-5-yl]-estradiol17alpha-Ethynylestradiol (0.25 mmol, 74 mg), diethyl 2,2-(diprop-2-ynyl)-l,3-propandioate (0.3 mmol, 70.8 mg), RhCI(PPh3)3 (0.025 mmol, 23 mg). Column chromatography on silica gel (2/1 hexan/EtOAc) yielded 75 mg (56%) of a colorless compound. i M.p. 164-C; [alpha]D = +35" (c 0.022 g/ml, acetone); H NMR (400 MHz, C6D6) delta 0.71-0.79 (m, IH),0.87 (t, J = 6.8 Hz, 3H), 0.88 (t, J = 6.8 Hz, 3H), 1.06 (s, 3H), 1.03-1.12 (m, IH), 1.29-1.42 (m, 4H), 1.61-1.75 (m, 4H), 1.88-2.00 (m, 2H), 2.18-2.23 (m, IH)1 2.58-2.70 (m, 2H), 3.73-3.85 (m, 4H), 3.91 (q, J = 6.8 Hz, 2H), 3.92 (q, J = 6.8 Hz, 2H), 5.14 (s, IH), 6.47 (d, J = 2.8 Hz, IH), 6.57 (dd, J = 8, 2.8 Hz, IH), 6.94 (d, J = 8 Hz, IH), 7.04 (d, J = 8 Hz, IH), 7.164 (s, IH) signal overlapped, 7.37 (s,IH); C NMR (100 MHz, C6D6) delta 14.60 (2x), 15.74, 25.05, 27.33, 28.46, 30.62, 34.67, 39.63, 40.46, 41.37, 41.76, 44.20, 47.83, 49.15, 61.66, 62.35(2x), 86.64, 113.73, 116.23, 123.90, 124.49, 127.40, 129.23, 133.05, 138.56, 139.50, 140.19, 146.60, 155.06, 172.47 (2x); IR (ATR ZnSe) v 3398, 2958, 2927, 2870, 1727, 1711, 1610, 1502, 1442, 1283, 1249, 1185, 1068, 1049, 1008 cm ; MS (El) 532 (8), 514 (72), 499 (17), 425 (17), 314 (12), 213 (56), 149 (77); HRMS (El) calculated for C33H40O6532.282489, found 532.283226.
  • 66
  • [ 2689-88-5 ]
  • [ 82203-84-7 ]
  • [ 1225289-34-8 ]
YieldReaction ConditionsOperation in experiment
90% With ferrous iodide; zinc In acetonitrile at 80℃; for 12h;
90% With ferrous iodide; zinc In acetonitrile at 80℃; for 12h;
83% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
20 %Spectr. With rhodium(III) chloride trihydrate; N-ethyl-N,N-diisopropylamine In toluene for 18h; Reflux;

  • 67
  • [ 2689-88-5 ]
  • [ 1309866-36-1 ]
  • [ 1309866-37-2 ]
YieldReaction ConditionsOperation in experiment
56% With bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butyl-4-methylpyridine In acetonitrile at 20℃; for 2h; Inert atmosphere;
  • 68
  • [ 2689-88-5 ]
  • ethyl 2-cyanothiazole-4-carboxylate [ No CAS ]
  • [ 1315323-58-0 ]
YieldReaction ConditionsOperation in experiment
93% With chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) In dichloromethane at 20℃; for 20h; Inert atmosphere; regioselective reaction;
  • 69
  • [ 18180-30-8 ]
  • [ 2689-88-5 ]
  • [ 1214275-10-1 ]
  • 70
  • [ 2689-88-5 ]
  • [ 1214275-07-6 ]
  • [ 1214275-12-3 ]
YieldReaction ConditionsOperation in experiment
91% With cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 40℃; Inert atmosphere;
  • 71
  • [ 2689-88-5 ]
  • [ 2499-64-1 ]
  • [ 1214275-11-2 ]
YieldReaction ConditionsOperation in experiment
94% With cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 40℃; Inert atmosphere;
  • 72
  • [ 2689-88-5 ]
  • [ 10401-11-3 ]
  • [ 1214275-19-0 ]
YieldReaction ConditionsOperation in experiment
99% With cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 40℃; Inert atmosphere;
  • 73
  • [ 2689-88-5 ]
  • [ 13861-22-8 ]
  • [ 1214275-15-6 ]
YieldReaction ConditionsOperation in experiment
97% With cobalt(II) chloride hexahydrate; 2-(2,6-diisopropylphenyliminomethyl)pyridine; zinc In tetrahydrofuran at 40℃; Inert atmosphere;
  • 74
  • [ 2689-88-5 ]
  • [ 1354526-76-3 ]
YieldReaction ConditionsOperation in experiment
99% Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With potassium carbonate In acetonitrile at 20℃; for 0.5h; Inert atmosphere; Stage #2: With water-d2 In acetonitrile at 20℃; for 1h; Inert atmosphere;
  • 75
  • [ 2689-88-5 ]
  • [ 33491-05-3 ]
  • [ 1577232-61-1 ]
YieldReaction ConditionsOperation in experiment
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran for 12h; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 2.2 (2) 80 mmol of compound 1 and 200 mmol of p-methylphenylethynyl bromide are mixed in a dry, oxygen-free catalytic system of Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol) , Molar ratio Pd(PPh3)2Cl2: CuI=3:1,336 mmol of triethylamine was used as a base, 150 ml of anhydrous acetonitrile as solvent, The reaction was stirred at room temperature for 12 hours. The product was was washed H water, Extract with ethyl acetate, Drying under reduced pressure, Separation by column chromatography with a 1:40 volume ratio of ethyl acetate:petroleum ether gave the product as a pale yellow solid.That is, the precursor compound 4.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 20h; 2 The malonic acid diethyl hindered of the diyne compound (20 mmol) with methyl phenylacetylene bromine (40 mmol) is added to the bottle, to be mixed in the Pd (PPh3)2Cl2And CuI as a catalyst in the oxygen free of catalytic system, wherein the catalyst amount is 0.6 mmol, Pd (PPh3)2Cl2: CuI=3.2: 1. In order to three-ethylamine (60 mmol) as the base, in order to water-acetonitrile (25 ml) as the solvent, stirring at room temperature the reaction 20 hours, the reaction product is successively 15% hydrochloric acid solution, 10% sodium bicarbonate solution, saturated salt water by washing; then ethyl acetate extraction, pressure reducing turns on lathe does, column chromatography (eluent in ethyl acetate with petroleum ether of volume ratio of 1:50) to obtain the light brown colored solid product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 11h; 2.2 2) 80mmol compound 1 with200 mmol of phenylethynyl bromide mixed with Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol) in an anhydrous anaerobic catalytic system,Molar ratio Pd(PPh3)2Cl2: CuI=3:1, with 336 mmol of triethylamine as the base,The reaction was stirred at room temperature for 11 hours with 150 mL of anhydrous acetonitrile as a solvent, and the product was washed with water.Extract with ethyl acetate and spin dry under reduced pressure.Column chromatography (volume ratio ethyl acetate: petroleum ether = 1:80) gave a pale yellow solid product.That is, Compound 2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: 1-(2-bromoethynyl)-4-methylbenzene With triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 11h; 2.2 2) Mix 80mmol of compound 1 with 200mmol of p-toluene ethynyl bromide in an anhydrous anaerobic catalytic system (2.56mmol/0.85mmol) of Pd(PPh3)2Cl2/CuI, the molar ratio of Pd(PPh3)2Cl2/CuI=3 :1. Using 336mmol triethylamine as base, 150ml anhydrous acetonitrile as solvent, stirring and reacting at room temperature for 11 hours, the product was washed with water, extracted with ethyl acetate, spin-dried under reduced pressure, column chromatography (volume ratio ethyl acetate : Petroleum ether = 1:80) to obtain a pale yellow solid product, which is the precursor compound 2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Preparation of tetrayne substrate General procedure: 0.6 g Pd(PPh3)2Cl2, 0.5 g CuI and 40 mmol diyne substrate were added in 500 mL three-necked flask, protected with anhydrous anaerobic conditions under argon. After 0.5 h, 250-300 mL acetonitrile, 16.16 g Et3N and 100 mmol brominated aryl alkyne were added in turn, magnetically stirred for 10-12 h under ice-water bath. The organic phase was extracted with ethyl acetate and dried with anhydrous MgSO4. It was separated by column chromatography on silica gel to obtain tetrayne substrate as white solid finally.

  • 76
  • [ 2689-88-5 ]
  • [ 1345683-42-2 ]
  • [ 1577232-62-2 ]
YieldReaction ConditionsOperation in experiment
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran for 12h; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(II) iodide; triethylamine In acetonitrile at 25℃; for 14h; 2.2 80 mmol of compound a-2 and 240 mmol of phenylethynyl bromide were mixed in a dry oxygen free catalytic system (1.92 mmol / 0.64 mmol) of Pd (PPh3) 2Cl2 / CuI, the molar ratio of Pd (PPh3) 3: 1, 384mmol triethylamine as base, 100mL anhydrous acetonitrile as solvent, the reaction was stirred at 25 ° C for 14 hours, the product was washed with water, extracted with ethyl acetate, dried under reduced pressure, with a volume ratio of 1:50 Ethyl acetate: petroleum ether column chromatography to obtain a brown solid product, Compound b-2.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 20h; 2 Example 2 Diacetylene compounds (20 mmol), which are bridged with diethyl malonate,And p-ethyl phenylacetylene bromide (40mmol) was added to the reaction flask,Anhydrous and anaerobic catalytic systems were mixed with Pd (PPh3)2Cl and CuI as catalysts in amounts of 0.6 mmol and Pd (PPh3)2Cl2: Cul = 3.2: 1. With triethylamine (100 mmol) as base and anhydrous acetonitrile (25 mL) as solvent, the reaction was stirred at room temperature for 20 hours. The reaction product was washed with 15% hydrochloric acid solution, 10% sodium bicarbonate solution and saturated brine ; Then extracted with ethyl acetate, dried under reduced pressure and the residue was purified by column chromatography (eluent: ethyl acetate to petroleum ether 1:50 by volume) to give a light brown solid product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 4 Example 4 Diethylmalonate bridged diyne compound (20 mmol) and p-ethylphenylacetylene bromide (48 mmol) were added toIn the reaction flask,In the anhydrous oxygen-free catalytic system in which Pd(PPh3)2Cl2 and CuI are used as catalysts,The amount of catalyst was 0.6 mmol, Pd(PPh3)2Cl2:CuI=3:1.Triethylamine (100 mmol) was used as the base and anhydrous acetonitrile (40 mL) was used as the solvent.The reaction was stirred at room temperature for 12 hours, and the reaction product was successively treated with a 15% hydrochloric acid solution.10% sodium bicarbonate solution and saturated brine were separately washed; then extracted with ethyl acetate,Drying under reduced pressure,Column chromatography (volume ratio of ethyl acetate to petroleum ether in the eluent of 1:40) yielded a light brown solid product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 2.2 (2) Mix 80 mmol of compound 1 with 200 mmol of p-ethylphenylethynyl bromide in an anhydrous anaerobic catalytic system of Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol), molar ratio Pd(PPh3)2Cl2:CuI =3:1, use 336 mmol of triethylamine as a base and 150 ml of anhydrous acetonitrile as a solvent. The reaction was stirred at room temperature for 12 hours, and the product was washed with water, extracted with ethyl acetate, and dried under reduced pressure, with a volume ratio of 1:40. Ethyl acetate: petroleum ether column chromatography to give the product as a pale yellow solid. That is, the Precursor Compound 2, that is, tetrayne.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 2.2 (2) 80mmol of compound 1 was mixed with 200mmol of P-ethyl phenyl ethynyl bromide in an anhydrous anaerobic catalytic system of Pd (PPh3) 2CI2/CuI (2.56mmol/0.85mmol), molar ratio Pd (PPI13) 2CI2: Cul = 3:1, using 336mmol of triethylamine as a base, 150mL anhydrous acetonitrile as solvent, the reaction was stirred at room temperature for 12 hours, the product is washed with water, extract with ethyl acetate and spin dry under reduced pressure,separation with ethyl acetate: petroleum ether column chromatography at a volume ratio of 1:60, obtained a solid product
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Preparation of tetrayne substrate General procedure: 0.6 g Pd(PPh3)2Cl2, 0.5 g CuI and 40 mmol diyne substrate were added in 500 mL three-necked flask, protected with anhydrous anaerobic conditions under argon. After 0.5 h, 250-300 mL acetonitrile, 16.16 g Et3N and 100 mmol brominated aryl alkyne were added in turn, magnetically stirred for 10-12 h under ice-water bath. The organic phase was extracted with ethyl acetate and dried with anhydrous MgSO4. It was separated by column chromatography on silica gel to obtain tetrayne substrate as white solid finally.

  • 77
  • [ 2689-88-5 ]
  • [ 82203-83-6 ]
  • C23H23F3O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With ferrous iodide; zinc In acetonitrile at 80℃; for 12h;
83% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 78
  • [ 2689-88-5 ]
  • 4-(3,3,3-trifluoroprop-1-yn-1-yl)-1,1'-biphenyl [ No CAS ]
  • C28H25F3O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With ferrous iodide; zinc In acetonitrile at 80℃; for 12h;
81% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 79
  • [ 2689-88-5 ]
  • [ 101055-70-3 ]
  • C24H31O4P [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With ferrous iodide In m-xylene at 140℃; for 18h; Schlenk technique; Inert atmosphere;
80% With o-phenylenebis(diphenylphosphine); cobalt(II) iodide In tetrahydrofuran at 210℃; for 4h; Microwave irradiation; chemoselective reaction;
  • 80
  • [ 2689-88-5 ]
  • [ 919765-93-8 ]
  • C33H31O4P [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With ferrous iodide In m-xylene at 140℃; for 18h; Schlenk technique; Inert atmosphere;
23% With o-phenylenebis(diphenylphosphine); cobalt(II) iodide In tetrahydrofuran at 210℃; for 4h; Microwave irradiation; chemoselective reaction;
  • 81
  • [ 2689-88-5 ]
  • C11H12O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With ethanol; potassium hydroxide at 20℃; for 18h; 4.3.2. Synthesis of compound 5 Compound 4 (500 mg, 2.11 mmol) was dissolved in minimumamount of dry ethanol and then KOH (118 mg, 2.11 mmol) in 15 mL of dry ethanol was added slowly to the reaction mixture. The solution wasstirred at room temperature for the next 18 h. After that, the reactionmixture was washed with ethyl acetate and saturated sodium bicarbonatesolution and the aqueous layer was collected, followed by acidificationto pH < 1 of the solution. Then the solution was washed twicewith water and ethyl acetate and finally, the organic layer was collectedwhich was dried over reduced pressure to get pure white crystals with95% of yield.
90% With potassium hydroxide In ethanol chemoselective reaction;
  • 82
  • [ 2689-88-5 ]
  • [ 929616-31-9 ]
  • C39H48O12 [ No CAS ]
  • C28H30F3NO8 [ No CAS ]
  • diethyl 2-[[2,2-bis(ethoxycarbonyl)indan-5-yl]methyl]-2-(2-propynyl)malonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) In dichloromethane at 40℃; Ruthenium catalyzed cyclotrimerization (general procedure). General procedure: A solution of alkyne (1 equiv.) and Cp*Ru(Cod)Cl (3 mol.%) in anhydrous dichloroethane (10 mL) was thrice degassed upon cooling. The solution obtained was heated to 40° C, followed by a dropwise addition of a solution of 1,6diyne (2 equiv.) in anhydrous dichloroethane over 1 h. The reaction mixture was stirredat 40° C until the reaction reached completion (TLC monitoring). The solvent was evaporated at reduced pressure, the crude product was purified by column chromatography on silica gel(eluent dichloromethane-EtOAc or light petroleum-EtOAc).
  • 83
  • [ 2689-88-5 ]
  • [ 1228473-25-3 ]
  • C39H48O12 [ No CAS ]
  • C30H37F3NO9P [ No CAS ]
  • diethyl 2-[[2,2-bis(ethoxycarbonyl)indan-5-yl]methyl]-2-(2-propynyl)malonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) In dichloromethane at 40℃; Ruthenium catalyzed cyclotrimerization (general procedure). General procedure: A solution of alkyne (1 equiv.) and Cp*Ru(Cod)Cl (3 mol.%) in anhydrous dichloroethane (10 mL) was thrice degassed upon cooling. The solution obtained was heated to 40° C, followed by a dropwise addition of a solution of 1,6diyne (2 equiv.) in anhydrous dichloroethane over 1 h. The reaction mixture was stirredat 40° C until the reaction reached completion (TLC monitoring). The solvent was evaporated at reduced pressure, the crude product was purified by column chromatography on silica gel(eluent dichloromethane-EtOAc or light petroleum-EtOAc).
  • 84
  • [ 2689-88-5 ]
  • [ 1186-73-8 ]
  • 5,5-di(ethoxycarbonyl)-1,1-di(methoxycarbonyl)-1,4,5,6-tetrahydro-2H-inden-2-one [ No CAS ]
  • spiro-1-bis(5,5-di(ethoxycarbonyl)-1,4,5,6-tetrahydro-2H-inden-2-one) [ No CAS ]
  • 85
  • [ 2689-88-5 ]
  • [ 151589-34-3 ]
  • diethyl 5-cyano-6-(p-tolyl)-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With iron(II) chloride tetrahydrate; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc In 1,2-dimethoxyethane at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; chemoselective reaction;
84% With (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride In 1,2-dimethoxyethane at 20℃; for 0.5h; chemoselective reaction;
  • 86
  • [ 2689-88-5 ]
  • [ 14677-99-7 ]
  • diethyl 5-cyano-6-(4-methoxyphenyl)-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With iron(II) chloride tetrahydrate; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc In 1,2-dimethoxyethane at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; chemoselective reaction;
80% With (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride In 1,2-dimethoxyethane at 20℃; for 0.5h; chemoselective reaction;
  • 87
  • [ 2689-88-5 ]
  • [ 99337-57-2 ]
  • diethyl 5-cyano-6-hexyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With iron(II) chloride tetrahydrate; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc In 1,2-dimethoxyethane at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; chemoselective reaction;
  • 88
  • [ 2689-88-5 ]
  • [ 73606-42-5 ]
  • diethyl 5-cyano-6-(thiophen-3-yl)-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With iron(II) chloride tetrahydrate; 2-(((2,6-diisopropylphenyl)imino)methyl)pyridine; zinc In 1,2-dimethoxyethane at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; chemoselective reaction;
76% With (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride In 1,2-dimethoxyethane at 20℃; for 0.5h; chemoselective reaction;
  • 89
  • [ 2689-88-5 ]
  • [ 33491-03-1 ]
  • C29H22Cl2O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1 Example 1 Diacetylene bridged with diethyl malonateThe compound (20 mmol)versusP-ChlorobenzeneAcetylene bromine(48 mmol) was added to the reaction flask,Mixed in Pd (PPh3) 2Cl2 and CuI as a catalyst in the anhydrous anaerobic catalytic system,Wherein the amount of the catalyst is 0.8 mmol,Pd (PPh3) 2Cl2: CuI = 3: 1.Using triethylamine (50 mmol) as base,With anhydrous acetonitrile (40 mL) as solvent,The reaction was stirred at room temperature for 12 hours,The reaction product was washed with 15% hydrochloric acid solution,10% sodium bicarbonate solution, saturated brine were washed;Then extracted with ethyl acetate, dried under reduced pressure,Column chromatography (the volume ratio of ethyl acetate to petroleum ether in the eluent was 1:40) gave a light brown solid product.
Stage #1: diethyl 2,2-di(prop-2-yn-1-yl)malonate With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: 1-(bromoethynyl)-4-chlorobenzene With triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Schlenk technique;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 0℃; Inert atmosphere; Preparation of tetrayne substrate General procedure: 0.6 g Pd(PPh3)2Cl2, 0.5 g CuI and 40 mmol diyne substrate were added in 500 mL three-necked flask, protected with anhydrous anaerobic conditions under argon. After 0.5 h, 250-300 mL acetonitrile, 16.16 g Et3N and 100 mmol brominated aryl alkyne were added in turn, magnetically stirred for 10-12 h under ice-water bath. The organic phase was extracted with ethyl acetate and dried with anhydrous MgSO4. It was separated by column chromatography on silica gel to obtain tetrayne substrate as white solid finally.

  • 90
  • [ 2689-88-5 ]
  • [ 932-87-6 ]
  • [ 1577232-63-3 ]
YieldReaction ConditionsOperation in experiment
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 20℃; for 12h; 1.2 (2) 80 mmol of compound 1 and 200 mmol of phenylethynyl bromide are mixed in Pd(PPh3)2Cl2/CuI (2.56 mmol/0.85 mmol) anhydrous oxygen-free catalytic system.Molar ratio Pd(PPh3)2Cl2:CuI=3:1,336 mmol of triethylamine was used as a base,With 150mL anhydrous acetonitrile as solvent,The reaction is stirred at room temperature for 12 hours.The product is washed with water,Extract with ethyl acetate,Drying under reduced pressure,Separation by column chromatography with ethyl acetate: petroleum ether at a volume ratio of 1:60,A white solid product is obtained,Precursor compound 2,
  • 91
  • [ 2689-88-5 ]
  • [ 611-10-9 ]
  • C21H28O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With [Re2Br2(CO)6(tetrahydrofuran)2]; N-ethyl-N,N-diisopropylamine In octane at 80℃; for 24h;
  • 92
  • [ 2689-88-5 ]
  • [ 122961-10-8 ]
  • diethyl 6-(3-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil. 4.4.1. Diethyl 6-(3-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3 H)-dicarboxylate (5dA) Yield: 82%; Colorless oil; 1H NMR: δ 1.27 (t, J=7.1 Hz, 6 H), 3.65 (s, 2 H), 3.68 (s, 2 H), 4.23 (q, J=7.1 Hz, 4 H), 7.12 (s, 1 H), 7.18 (d, J=7.3 Hz, 1 H), 7.27-7.37 (m, 3 H), 7.57 (s, 1 H); 13C NMR: δ 14.1, 40.2, 40.4, 60.5, 62.1, 122.1 (q, J=5.3), 124.2 (q, J=273.7 Hz), 127.4 (d, J=1.1 Hz), 127.5 (q, J=29.6 Hz), 127.75, 127.80, 129.0, 129.2 (d, J=1.3 Hz), 133.7, 139.0, 140.2, 141.7, 144.1, 171.3; 19F NMR: δ -56.90 (s, 3 F); IR (neat): ν 1734, 1346, 1297, 1281, 1247, 1205, 1190, 1156, 1136, 1124, 1097, 1065 cm-1; HRMS (FAB): calcdfor [M+H]+ C22H21ClF3O4: 441.1080, Found: 441.1096.
  • 93
  • [ 2689-88-5 ]
  • [ 122247-01-2 ]
  • diethyl 6-(2-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 94
  • [ 2689-88-5 ]
  • [ 573979-96-1 ]
  • diethyl 6-(4-ethoxycarbonylphenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 95
  • [ 2689-88-5 ]
  • 3,3,3-trifluoro-1-(dimethylphenylsilyl)propyne [ No CAS ]
  • diethyl 6-dimethylphenylsilyl-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 96
  • [ 2689-88-5 ]
  • 1-(4-chlorophenyl)-2-perfluorobutyl acetylene [ No CAS ]
  • diethyl 6-(4-chlorophenyl)-5-nonafluorobutyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 97
  • [ 2689-88-5 ]
  • [ 96302-93-1 ]
  • diethyl 6-(1-hydroxycyclohexan-1-yl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
46% With CoCl2((S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl); zinc(II) iodide; zinc In acetonitrile at 80℃; for 3h; Inert atmosphere; Glovebox; 4.4. Typical procedure for the cobalt-catalyzed cycloaddition of fluoroalkylated alkynes with diynes General procedure: In a nitrogen-filled glove box, a 30 mL two-necked round-bottomed flask, equipped with a magnetic stirring bar, was charged with zinc iodide (0.016 g, 0.050 mmol). Subsequently the flask was taken out of the gloved box and zinc powder (0.033 g, 0.50 mmol), fluorinated alkyne 1a (0.123 g, 0.60 mmol), diethyl dipropargylmalonate 4A (0.117 g, 0.50 mmol), and acetonitrile (1.5 mL) were added to the mixture. The resulting mixture was stirred at 80 °C with an oil bath. After 3 h, the reaction mixture was subjected to flash column chromatography using silica gel as stationary phase and CH2Cl2 as mobile phase. After removal of solvent from the eluent under reduced pressure, the residue was purified by column chromatography (hexane/AcOEt=10/1) to give diethyl 6-(4-chlorophenyl)-5-trifluoromethyl-1H-indene-2,2(3H)-dicarboxylate 5 aA in 83% yield (0.181 g, 0.41 mmol) as colorless oil.
  • 98
  • [ 2689-88-5 ]
  • [ 1942-45-6 ]
  • C21H30O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
58% With dicobalt octacarbonyl In toluene at 230℃; Flow reactor;
  • 99
  • [ 2689-88-5 ]
  • [ 1345683-42-2 ]
  • C29H32O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 20℃; for 11h; 3.2 (2) 80 mmol of compound a-3Mixed with 200 mmol of p-ethylphenylethynyl bromide,In Pd(PPh3)2Cl2/CuIIn an anhydrous anoxic catalytic system,Molar ratio Pd(PPh3)2Cl2: CuI=3:1; Pd(PPh3)2Cl2The amount of CuI is 2.56 mmol,0.85mmo, with 336mmol of triethylamine as a base,150mL anhydrous acetonitrile as solventThe reaction was stirred at room temperature for 11 hours.The product is washed with water,Extracted with ethyl acetate,Dry under reduced pressure,In a volume ratio of ethyl acetate:Column chromatography with petroleum ether = 1:70 as eluent.After concentration and drying under reduced pressure,Obtaining a pale yellow solid product precursor compound b-3;
  • 100
  • [ 2689-88-5 ]
  • [ 40870-15-3 ]
YieldReaction ConditionsOperation in experiment
90% With lithium chloride In water; dimethyl sulfoxide for 1h; Reflux; 7.2 Step 2: Synthesis of ethyl 2-(prop-2-yn-l-yl)pent-4-ynoate Dimethyl 2,2-di(2-propynyl)malonate (4.70 g, 22.6 mmol) and lithium chloride (0708) (2.95 g, 69.7 mmol) were dissolved in a solution of H2O (1.0 mL, 55.5 mmol) and DMSO (40 mL). This solution was then heated to reflux for 1 h. After cooling, the reaction mixture was poured into CHCI3 (40 mL) and H2O (40 mL). The layers were separated and the aq layer was extracted with CHCI3 (3 x 40 mL). The combined organic layers were washed with H2O (50 mL) and brine (50 mL), dried, filtered through silica gel, and concentrated, leaving a yellow oil. The crude oil was purified by flash chromatography on a silica gel column using 20% EtOAc in hexanes as the eluent resulting in 3.06 g of a pale yellow oil (90% yield).
90% With lithium chloride In water; dimethyl sulfoxide for 1h; Reflux; 22.2 Step 2: Synthesis of ethyl 2-(prop-2-yn-1-yl)pent-4-ynoate. Dimethyl 2,2-di(2-propynyl)malonate (4.70 g, 22.6 mmol) and lithium chloride (2.95 g, 69.7 mmol) were dissolved in a solution of H2O (1.0 mL, 55.5 mmol) and DMSO (40 mL). This solution was then heated to reflux for 1 h. After cooling, the reaction mixture was poured into CHCl3 (40 mL) and H2O (40 mL). The layers were separated and the aq layer was extracted with CHCl3 (3 × 40 mL). The combined organic layers were washed with H2O (50 mL) and brine (50 mL), dried, filtered through silica gel, and concentrated, leaving a yellow oil. The crude oil was purified by flash chromatography on a silica gel column using 20% EtOAc in hexanes as S4 the eluent resulting in 3.06 g of a pale yellow oil (90% yield).
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