Claims
- 1. A process for preparing a compound of formula 12
- 2. The process of claim 1, wherein the base is selected from the group consisting of 4-dimethylaminopyridine, triethylamine, and combinations thereof.
- 3. The process of claim 1 or 2, wherein the 17-O-(chloromethyldimethylsilyl) derivative is treated with a lithium dialkylamide.
- 4. The process of any of claims 1-3, wherein the 17-O-(chloromethyldimethylsilyl) derivative is treated with lithium diisopropylamide.
- 5. A process for preparing a compound of formula 13
- 6. The process of claim 6, wherein the selective ketalization is carried out by treating the compound of formula 5 with ethylene glycol, triethylorthoformate, and an acid.
- 7. The process of claim 5 or 6, wherein the selective ketalization is carried out at a temperature of about 30° C. or below.
- 8. A process for preparing a compound of formula 14
- 9. The process of claim 8, wherein the selective methylation is carried out by treating the compound of formula 13 with a trimethyloxonium salt.
- 10. The process of claim 8 or 9, wherein the selective methylation is carried out by treating the compound of formula 13 with trimethyloxonium tetrafluoroborate.
- 11. A process for preparing a compound of formula 15
- 12. The process of claim 11, wherein the reduction is carried out by treating the compound of formula 14 with a hydride.
- 13. The process of claim 11 or 12, wherein the reduction is carried out by treating the compound of formula 14 with lithium aluminum hydride.
- 14. A process for preparing a 5α,10α-compound of formula 16
- 15. The process of claim 14, wherein the oxidation is carried out by treating the compound of formula 15 with an adduct formed from a hexahaloacetone and a peroxide in the presence of a weak base.
- 16. The process of claim 14 or 15, wherein the oxidation is carried out by treating the compound of formula 14 with an adduct formed from hexafluoroacetone and hydrogen peroxide in the presence of a weak base.
- 17. A process for preparing a compound of formula 17
- 18. The process of claim 17, wherein the cuprous halide is cuprous chloride.
- 19. The process of claim 17 or 18, wherein the Grignard reagent is prepared from 4-bromo-N,N-dimethylaniline and magnesium.
- 20. The process of any of claims 17-19, wherein the cuprous halide is oxidized by air.
- 21. A process for preparing a compound of formula 18
- 22. The process of claim 21, wherein the deketalization is carried out by treating the compound of formula 17 with an organic acid.
- 23. The process of claim 21 or 22, wherein the deketalization is carried out by treating the compound of formula 17 with acetic acid.
- 24. A process for preparing a compound of formula 10
- 25. The process of claim 24, wherein the selective oxidation is carried out by treating the compound of formula 18 with 2-iodoxybenzoic acid.
- 26. A process for preparing a compound of formula 11
- 27. The process of claim 26, wherein the cyanohydrin group is replaced with a chloroacetyl group with a 17α-hydroxyl group in a one-pot Silicon Nucleophilic Annelation process reaction.
- 28. The process of claim 26 or 27, wherein the cyanohydrin group is replaced by treating the compound of formula 1 with chloro(chloromethyl)-dimethylsilane and a base to obtain a 17-O-(chloromethyldimethylsilyl) derivative of the compound of formula 1 and treating the 17-O-(chloromethyldimethylsilyl) derivative with an alkali metal dialkylamide.
- 29. The process of any of claims 26-28, wherein the selective ketalization of the compound of formula 5 is carried out at a temperature below about 30° C.
- 30. The process of any of claims 26-29, wherein the epoxidation is carried out by treating the compound of formula 15 with hexafluoroacetone and hydrogen peroxide in the presence of a weak base.
- 31. The process of any of claims 26-30 including trituration of the resulting crude product of the compound of formula 16 with an ether.
- 32. The process of any of claims 26-31, wherein the introduction of the N,N-dimethylaminophenyl group at the 11β-position with the concomitant opening of the epoxide ring of the compound of formula 16 is carried out by treating the compound of formula 16 with a Grignard reagent in the presence of a cuprous halide, quenching the Grignard reaction mixture with an ammonium salt, and oxidizing the cuprous halide to cupric halide.
- 33. The process of any of claims 26-32, wherein the selective oxidation of the 20-hydroxyl group is carried out by treating the compound of formula 18 with 2-iodoxybenzoic acid.
- 34. The process of any of claims 26-33, wherein the acetylation of the compound of formula 10 is carried out by treating the compound with trifluoroacetic anhydride, acetic acid, and p-toluenesulfonic acid.
- 35. A compound of the formula:
- 36. A compound of the formula:
- 37. A compound of the formula:
- 38. A compound of the formula:
- 39. A compound of the formula:
- 40. A compound of the formula:
- 41. A compound of the formula:
- 42. A process for selectively oxidizing the secondary alcohol group of a composition containing secondary and tertiary alcohol groups comprising treating the composition with a haloxybenzoic acid.
- 43. The process of claim 42, wherein said composition is an organic compound.
- 44. The process of claim 42 or 43, wherein the haloxybenzoic acid is 2-iodoxybenzoic acid.
CROSS-REFERENCE TO A RELATED APPLICATION
[0001] This application claims the benefit of U.S. provisional patent application No. 60/173,470, filed Dec. 29, 1999, the disclosure of which is incorporated by reference in its entirety.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
PCT/US00/35479 |
12/29/2000 |
WO |
|