aluminum;2-methylpropan-2-olate

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40t) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3 H, s, 18-CH3), 0.90 (3 H, d, 21-CH3), 1.17 (3 H, S, 19-CH3), 3.66 (3 H, s, CO2CH3 and 5.71 (1 H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 30β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3) 0.90 (3H, d, 21-CH3), 1.17 (3H, S, l9-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3) 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

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

Procedure: A mixture of 1,1,1-triethoxyisobutane (27.5 g, 0.14 mol) and aluminium t-butoxide (30 g, 0.12 mol) was heated at 170° C. for 1 hour during which time t-butanol distilled off. The residue was distilled at 100°-130° C. (atomosphere pressure) to afford 12.1 g (58%) of 1,1-diethoxy-2,2-dimethylethylene (Formula III: R2 =R3 =CH3 ;R4 =R5 =OC2H5), as a clear oil. distilled off The residue was distilled at 100°-130° C. (atomosphere pressure)

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

Procedure: A mixture of 1,1,1-triethoxyisobutane (27.5 g, 0.14 mol) and aluminium t-butoxide (30 g, 0.12 mol) was heated at 170° C. for 1 hour during which time t-butanol distilled off. The residue was distilled at 100°-130° C. (atomosphere pressure) to afford 12.1 g (58%) of 1,1-diethoxy-2,2-dimethylethylene (Formula III: R2 =R3 =CH3 ;R4 =R5 =OC2H5), as a clear oil. distilled off The residue was distilled at 100°-130° C. (atomosphere pressure)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40%) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl) δ: 0.71 (3H, s, 18-CH3), 0.90 (3H, d, 21-CH3), 1.17 (3H, S, 19-CH3), 3.66 (3H, s, CO2CH3) and 5.71 (1H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3β-hydroxy-5-cholenic acid methyl ester 3001 (24.16 g, 57.11 mmol), aluminum tri-t-butoxide (56.27 g, 228.43 mmol) and isopropylmethylketone (50 ml) in dry toluene (150 ml) was stirred and heated to 120° C. (oil bath) for 6 hours. The reaction mixture was then cooled to room temperature diluted with toluene (100 ml) and acidified with 2NHCl (70 ml). The organic layer was separated, and the aqueous layer extracted with toluene (3×50 ml). The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m), dried (MgSO4), filtered and evaporated in vacuo to get the crude product. Flash chromatography of the crude product using toluene followed by a gradient of ethyl acetate/hexane (5, 10, 20 and 40t) solvent systems gave a pure white solid, 3-oxo-4-cholenic acid methyl ester 3002 (13.43 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 0.71 (3 H, s, 18-CH3), 0.90 (3 H, d, 21-CH3), 1.17 (3 H, S, 19-CH3), 3.66 (3 H, s, CO2CH3 and 5.71 (1 H, s, 4-H). The reaction mixture was then cooled to room temperature The organic layer was separated the aqueous layer extracted with toluene (3×50 ml) The combined organic extracts were washed with water (1×50 ml), saturated NaHCO3 (2×50 ml), water (1×50 ml), brine (1×50 m) dried (MgSO4) filtered evaporated in vacuo to get the crude product