(3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-ol

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

Procedure: 2.5 Millimole of 3β-cholestanol was dissolved in 50 ml of diethyl ether, and MCOsOx containing osmium tetroxide in an amount equivalent to 2.5 mmol was added thereto, followed by stirring at 25° C. for 30 hours to cause a reaction to take place. MCOsOx was removed from the reaction solution, and a crude keto compound was recovered from the filtrate and purified by silica gel column chromatography (eluent:benzene) to give 3-cholestanon at a yield of 90%. was added a reaction MCOsOx was removed from the reaction solution a crude keto compound was recovered from the filtrate purified by silica gel column chromatography (eluent:benzene)

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

Procedure: (R)-2-octanol (6a), Example 13: (1S, 2S, 3S, 5R)-(−)-isopinocampheol (7a), Example 14: (1R, 2R, 3R, 5S)-(−)-isopiriocampheol (8a), Example 15: β-cholestanol (9a) and Example 16: α-cholestanol (10a).

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

Procedure: (R)-2-octanol (6a), Example 13: (1S, 2S, 3S, 5R)-(−)-isopinocampheol (7a), Example 14: (IR, 2R, 3R, 5S)-(−)-isopinocampheol (8a), Example 15: β-cholestanol (9a) and Example 16: (α-cholestanol (10a).

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

Procedure: 3β-cholestanol (1.23 g, 3.16 mmol) was completely dissolved in anhydrous toluene (7 mL, 0.45 M) at r.t. Powdered potassium t-butoxide (1.06 g, 9.49 mmol, 3 eq) was added in one portion. The mixture was stirred at r.t. for 3 h. A solution of propargyl bromide (80 wt % in toluene, 0.94 g, 6.32 mmol, 2 eq) was added. The mixture was stirred at r.t. for 3 days. The mixture was diluted with hexane (30 mL) and EtOAc (10 mL), washed with water (2×60 mL) and brine (60 mL). The aqueous phase was extracted once with EtOAc (20 mL). The combined organic phases were dried (Na2SO4), filtered and the filtrate was evaporated onto silica gel and purified by column chromatography (silica gel 2.5×24 cm, gradient elution with hexane 250 mL, hexane-EtOAc 125:5) to give the product as a yellow solid. Recrystallization from EtOAc (3 mL) gave off-white crystals (736 mg, 55%). 1H NMR (CDCl3, 400 MHz) δ 4.18 (d, 2H, J=2.2), 3.45 (m, 1H), 2.38 (t, 1H, J=2.2), 1.99-0.57 (m, 31H), 0.89 (d, 3H, J=6.6), 0.86 (d, 3H, J=6.6), 0.86 (d, 3H, J=6.6), 0.79 (s, 3H), 0.64 (s, 3H). The mixture was stirred at r.t. for 3 days washed with water (2×60 mL) and brine (60 mL) The aqueous phase was extracted once with EtOAc (20 mL) The combined organic phases were dried (Na2SO4) filtered the filtrate was evaporated onto silica gel purified by column chromatography (silica gel 2.5×24 cm, gradient elution with hexane 250 mL, hexane-EtOAc 125:5)

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

Procedure: A solution of the fluorobenzoate (46, 27 mg, 0.051 mmol) in THF (2 mL) and MeOH (2 mL) was treated with 1M NaOH (0.2 mL, 0.2 mmol) and allowed to stand at ambient temperature for 7 h. After the solvent was evaporated, the residue was treated with CHCl3 (40 mL) and 10% Na2CO3 solution (30 mL); we then separated the layers, dried the organic layer over MgSO4, and filtered and evaporated it under reduced pressure. Purified on 2 g of Merck grade 60 flash silica gel using MeOH/CHCl3 (5:95) afforded 13 mg (60%) of 25-fluoro-3β-ol (47), mp 196°-198° C. EIMS (m/z): 428 (M+H), 413 (M-M3). 1H NMR: δ3.70 (m, 1H), 1.49 (s, 3H), 1.27 (s, 3H), 1.09 (s, 3H), 1.02 (d, 3H, J=6.4 Hz), 0.81 (s, 3H). After the solvent was evaporated the residue was treated with CHCl3 (40 mL) and 10% Na2CO3 solution (30 mL) we then separated the layers dried the organic layer over MgSO4 filtered evaporated it under reduced pressure Purified on 2 g of Merck grade 60 flash silica gel

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

Procedure: A solution of pyridazine 12 (113 mg, 0.22 mmol) in THF (1 mL) and MeOH (2 mL) was treated with 1M NaOH (0.29 mL, 0.29 mmol) and allowed to stand at ambient temperature for 16 h. The solvent was evaporated at reduced pressure and the residue was treated with CH2Cl2 (50 mL) and a 10% Na2CO3 solution (20 mL). The organic layer was separated, dried over MgSO4, filtered, and evaporated to dryness. The residue was purified by flash chromatography on 4 g of silica gel 60 using MeOH/CHCl3 (5:95) giving 65 mg (72%) of 13, which crystallized from CH2Cl2 /acetone, mp 203°-205° C. 1H NMR: δ3.71 (m, 1H), 3.13 (dd, 1H, J=5.6, 13.4 Hz), 3.10 (dd, 1H, J=6.8, 16.5 Hz), 2.95 (dd, 1H, J=10.6, 16.3 Hz), 2.61 (dd, 1H, J=12.8, 17.9 Hz), 2.27 (dd, 1H, J=6.1, 11.0 Hz), 2.23 (ddd, 1H, J=3.6, 3.6, 13.4 Hz), 1.06 (s, 3H), 0.99 (d, 3H, J=6.2 Hz), 0.89 (d, 6H, J=6.6 Hz), 0.80 (s, 3H). IR (Nujol): 3301, 1626, 1554, 1035 cm-1. EIMS (m/z): 410 (M+), 395 (M-Me). Anal. (C27H42N2O): C, H, N. The solvent was evaporated at reduced pressure the residue was treated with CH2Cl2 (50 mL) The organic layer was separated dried over MgSO4 filtered evaporated to dryness The residue was purified by flash chromatography on 4 g of silica gel 60 using MeOH/CHCl3 (5:95)

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

Procedure: 2.5 Millimole of 3β-cholestanol was dissolved in 50 ml of diethyl ether, and MCOsOx containing osmium tetroxide in an amount equivalent to 2.5 mmol was added thereto, followed by stirring at 25° C. for 30 hours to cause a reaction to take place. MCOsOx was removed from the reaction solution, and a crude keto compound was recovered from the filtrate and purified by silica gel column chromatography (eluent:benzene) to give 3-cholestanon at a yield of 90%. was added a reaction MCOsOx was removed from the reaction solution a crude keto compound was recovered from the filtrate purified by silica gel column chromatography (eluent:benzene)