trimethyl(2-trimethylsilylethynyl)silane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 19.5 g (0.1 M) of methyl N-carbethoxy-2-chloroglycinate and 17.0 g (0.1 M) of bis-trimethylsilyl acetylene in 200 ml of methylene chloride at 0° C is added 13.5 g (0.1 M) of aluminum chloride and the reaction mixture is allowed to warm to 25° C. After 24 hours at 25° C water is carefully added to the mixture which is then extracted with methylene chloride. The combined organic solutions are dried over magnesium sulfate, concentrated and distilled with the b.p. 100°/0.15 mm fraction collected to give methyl 2-trimethylsilylacetylene-2-carbethoxyaminoacetate. is then extracted with methylene chloride The combined organic solutions are dried over magnesium sulfate concentrated distilled with the b.p. 100°/0.15 mm fraction collected

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of bis(trimethylsilyl)acetylene and allyl isocyanate in dry solvent is treated with an excess (at least 2 molar equivalents) of an acid catalyst. The preferred acid catalysts include aluminum chloride, ferric chloride and methanesulfonic acid; the most preferred acid catalyst is methanesulfonic acid. Acid catalysts which have been found not to work include: titanium tetrachloride, zinc chloride (in diethyl ether), Amberlyst 15 and Dowex 50 ion exchange resins, and gaseous hydrochloric acid in dioxane. 1,2-dichloroethane and o-dichlorobenzene are preferred solvents, the most preferred solvent is dichloromethane. The concentration of bis(trimethylsilyl) acetylene in the above reaction is preferred to be 1 molar or lower. The reaction is monitored by gas chromatography, and when product formation is complete the mixture is poured into water or saturated sodium bicarbonate and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over sodium sulfate, filtered and evaporated to give an oil. When methanesulfonic acid is used as the catalyst, the oil may be used without further purification. When aluminum chloride is used as the catalyst, the oil is distilled under vacuum in a Kugelrohr apparatus (from about 100 to about 130° C. at from about 0.5 to about 1.0 Torr) to give the N-allyl-3-trimethylsilylpropiolic amide. ##STR9## wherein TMS is trimethylsilyl. extracted with ethyl acetate The organic phase is washed with water and brine dried over sodium sulfate filtered evaporated to give an oil the oil may be used without further purification the oil is distilled under vacuum in a Kugelrohr apparatus (from about 100 to about 130° C. at from about 0.5 to about 1.0 Torr)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3.40 g (20.0 mmol) of bis(trimethylsilyl)acetylene and 4.03 g (15.0 mmol) of 3,5-di-t-butyl-4-hydroxybenzoyl chloride [which is prepared from 3,5-di-t-butyl-4-hydroxybenzoic acid by treatment with oxalyl chloride (benzene, 60°, 2h)] in 80 mL of methylene chloride is treated at -78° with 1.78 mL (16.5 mmol) of titanium tetrachloride. The resulting dark mixture is stirred at -78° for 30 minutes and then is allowed to warm to 0° and stirred for an additional 30 minutes. The reaction solution is poured into 3N HCl and the layers are separated. The aqueous portion is extracted with pentane and the combined organic phase is washed with sat. NaCl and dried (MgSO4). The crude silylacetylene intermediate is concentrated, dissolved in 100 mL of methanol and then is treated at room temperature with 20 mL of 0.01M borax. After stirring the mixture at 25° overnight, it is poured into 3N HCl and the aqueous layer is extracted with pentane. The combined organic phase is washed with sat. NaCl and dried (MgSO4). Recyrstallization from hexane affords 2.40 g (62%) of the title compound: mp 100°-101°; IR (CCl4) 3620(s), 3300(m), 2950(s), 2090(m), 1640(s), 1580(s), 1290(s), 1215(vs) cm-1 ; 1H-NMR (CDCl3)δ(ppm) 1.45(s, 18H), 3.30(s, 1H), 5.80(s, 1H), 8.00(s, 2H); 13C-NMR (CDCl3)δ30.09, 34.41, 79.84, 80.80, 127.76, 128.51, 136.34, 160.02, 176.67 ppm. to warm to 0° stirred for an additional 30 minutes the layers are separated The aqueous portion is extracted with pentane the combined organic phase is washed with sat. NaCl dried (MgSO4) The crude silylacetylene intermediate is concentrated dissolved in 100 mL of methanol is treated at room temperature with 20 mL of 0.01M borax After stirring the mixture at 25° overnight, it is poured into 3N HCl the aqueous layer is extracted with pentane The combined organic phase is washed with sat. NaCl dried (MgSO4)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3.40 g (20.0 mmol) of bis(trimethylsilyl)acetylene and 4.03 g (15.0 mmol) of 3,5-di-t-butyl-4-hydroxybenzoyl chloride [which is prepared from 3,5-di-t-butyl-4-hydroxybenzoic acid by treatment with oxalyl chloride (benzene, 60°, 2h)] in 80 mL of methylene chloride is treated at -78° with 1.78 mL (16.5 mmol) of titanium tetrachloride. The resulting dark mixture is stirred at -78° for 30 minutes and then is allowed to warm to 0° and stirred for an additional 30 minutes. The reaction solution is poured into 3N HCl and the layers are separated. The aqueous portion is extracted with pentane and the combined organic phase is washed with sat. NaCl and dried (MgSO4). The crude silylacetylene intermediate is concentrated, dissolved in 100 mL of methanol and then is treated at room temperature with 20 mL of 0.01M borax. After stirring the mixture at 25° overnight, it is poured into 3N HCl and the aqueous layer is extracted with pentane. The combined organic phase is washed with sat. NaCl and dried (MgSO4). Recyrstallization from hexane affords 2.40 g (62%) of the title compound: mp 100°-101°; IR (CCl4) 3620(s), 3300(m), 2950(s), 2090(m), 1640(s), 1580(s), 1290(s), 1215(vs) cm-1 ; 1H-NMR (CDCl3)δ(ppm) 1.45(s, 18H), 3.30(s, 1H), 5.80(s, 1H), 8.00(s, 2H); 13C-NMR (CDCl3)δ30.09, 34.41, 79.84, 80.80, 127.76, 128.51, 136.34, 160.02, 176.67 ppm. to warm to 0° stirred for an additional 30 minutes the layers are separated The aqueous portion is extracted with pentane the combined organic phase is washed with sat. NaCl dried (MgSO4) The crude silylacetylene intermediate is concentrated dissolved in 100 mL of methanol is treated at room temperature with 20 mL of 0.01M borax After stirring the mixture at 25° overnight, it is poured into 3N HCl the aqueous layer is extracted with pentane The combined organic phase is washed with sat. NaCl dried (MgSO4)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: As directed by D. R. M. Walton and F. Waugh, J. Organomet. Chem. 37, 45 (1972), bis(trimethylsilyl)acetylene is acylated with cyclohexylacetic acid chloride and hydrolysed with aqueous/methanolic borax solution to 1-cyclohexyl-3-butyn-2-one. Reduction with (S)-B-(3-pinanyl)-9-borabiccyclo[3.3.1]nonane ((S)-Alpine-BoraneR, Aldrich, 88% ee) as directed by M. M. Midland et al., Tetrahedron 40, 1371 (1984) yields 1-cyclohexyl-3-butyn-2(S)-ol.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Amino-3-iodo-N-methyl-benzeneacetamide (7) (7.26 g, 0.025 mol), bis(trimethylsilyl) acetylene (8.52 g, 0.05 mol) and tetrakistriphenylphosphine Pd(O) (2.89 g, 0.0025 mol) were dissolved in CH3CN (400 mL) followed by the addition of saturated aqueous NaHCO3 (30 mL). The mixture was heated at reflux for 24 h. The solvent was removed in vacuo and the residue was dissolved in EtOAc. The organic phase was extracted with brine, dried over MgSO4, filtered and concentrated in vacuo. Silica gel chromatography (50-100% EtOAc gradient in hexane) of the concentrate afforded the product (8) (2.52 g, 38.8%) as a yellow viscous oil. The mixture was heated at reflux for 24 h The solvent was removed in vacuo the residue was dissolved in EtOAc The organic phase was extracted with brine dried over MgSO4 filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Amino-3-iodo-N-methyl-benzeneacetamide (7) (7.26 g, 0.025 mol), bis(trimethylsilyl) acetylene (8.52 g, 0.05 mol) and tetrakistriphenylphosphine Pd(O) (2.89 g, 0.0025 mol) were dissolved in CH3CN (400 mL) followed by the addition of saturated aqueous NaHCO3 (30 mL). The mixture was heated at reflux for 24 h. The solvent was removed in vacuo and the residue was dissolved in EtOAc. The organic phase was extracted with brine, dried over MgSO4, filtered and concentrated in vacuo. Silica gel chromatography (50-100% EtOAc gradient in hexane) of the concentrate afforded the product (8) (2.52 g, 38.8%) as a yellow viscous oil. The mixture was heated at reflux for 24 h The solvent was removed in vacuo the residue was dissolved in EtOAc The organic phase was extracted with brine dried over MgSO4 filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Amino-3-iodo-N-methyl-benzenemethanesulfonamide (1.63 g, 0.005 mol), bis(trimethylsilyl)acetylene (1.28 g, 0.0075 mol) and tetrakistriphenylphosphine Pd(O) (0.578 g, 0.0005 mol) were dissolved in DME (50 mL) and followed by the addition of saturated aqueous Na2CO3 (5 mL). The mixture was heated at reflux for 48 h. The solvent was removed in vacuo. The residue was dissolved in EtOAc and extracted with brine. The organic layer was dried over Na2SO4, filtered and evaporated in vacuo. Silica gel chromatography (10-100% EtOAc gradient in hexane) of the residue afforded the product (4) (1.08 g, 76.8%). The mixture was heated at reflux for 48 h The solvent was removed in vacuo The residue was dissolved in EtOAc extracted with brine The organic layer was dried over Na2SO4 filtered evaporated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Amino-3-iodo-N-methyl-benzenemethanesulfonamide (1.63 g, 0.005 mol), bis(trimethylsilyl)acetylene (1.28 g, 0.0075 mol) and tetrakistriphenylphosphine Pd(O) (0.578 g, 0.0005 mol) were dissolved in DME (50 mL) and followed by the addition of saturated aqueous Na2CO3 (5 mL). The mixture was heated at reflux for 48 h. The solvent was removed in vacuo. The residue was dissolved in EtOAc and extracted with brine. The organic layer was dried over Na2SO4, filtered and evaporated in vacuo. Silica gel chromatography (10-100% EtOAc gradient in hexane) of the residue afforded the product (4) (1.08 g, 76.8%). The mixture was heated at reflux for 48 h The solvent was removed in vacuo The residue was dissolved in EtOAc extracted with brine The organic layer was dried over Na2SO4 filtered evaporated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1,2-dimethoxyethane (DME, 70 mL) was added 2-iodo-4-[(methylsulfonyl)methyl]benzenamine (1) (1.9 g, 0.0061 mol), bis(trimethylsilyl) acetylene (1.56 g, 0.00915 mol), tetrakistriphenylphosphine Pd(O) (0.705 g, 0.00061 mol) and saturated aqueous Na2CO3 (5 mL). The reaction was heated at reflux for 48 h. The solvent was removed in vacuo and the residue was dissolved in EtOAc and washed with brine. The organic layer was dried over MgSO4, filtered and evaporated to give the crude product. Silica gel chromatography (20-100% EtOAc gradient in hexane followed by 5-10% MeOH gradient in EtOAc) of the concentrate afforded the product (2) (1.42 g, 83%) as a brown oil. The reaction was heated at reflux for 48 h The solvent was removed in vacuo the residue was dissolved in EtOAc washed with brine The organic layer was dried over MgSO4 filtered evaporated to give the crude product