Patent ID: 6281249
Filing Date: 2001-08-28
Classification: C07C,Y02P

Abstract:
A method of making a ketone of the formula ##STR10##where R is represented by the structure: ##STR11##where the stereochemical center at carbon 20 may have the R or S configuration, and where Z is selected from Y, --OY, --CH.sub.2 OY, --C.ident.CY and --CH.dbd.CHY, where the double bond may have the cis or trans geometry, and where Y is selected from hydrogen, methyl, --COR.sup.5 and a radical of the structure: ##STR12##where m and n, independently, represent the integers from 0 to 5, where R.sup.1 is selected from hydrogen, deuterium, hydroxy, protected hydroxy, fluoro, trifluoromethyl, and C.sub.1-5 -alkyl, which may be straight chain or branched and, optionally, bear a hydroxy or protected-hydroxy substituent, and where each of R.sup.2, R.sup.3 and R.sup.4, independently is selected from deuterium, deuteroalkyl, hydrogen, fluoro, trifluoromethyl and C.sub.1-5 alkyl, which may be straight-chain or branched, and optionally, bear a hydroxy or protected-hydroxy substituent, and where R.sup.1 and R.sup.2, taken together, represent an oxo group, or an alkylidene group, .dbd.CR.sup.2 R.sup.3, or the group --(CH.sub.2).sub.p --, where p is an integer from 2 to 5, and where R.sup.3 and R.sup.4, taken together, represent an oxo group, or the group --(CH.sub.2).sub.q --, where q is an integer from 2 to 5, and wherein any of the CH-groups at positions 20, 22, or 23 in the side chain may be replaced by a nitrogen atom, or where any of the groups --CH(CH.sub.3)--, --CH(R.sup.3)--, --CH(R.sup.2)-- at positions 20, 22 and 23, respectively, may be replaced by an oxygen or sulfur atom, and further wherein R.sup.5 is a protected-hydroxy group, which comprises the steps of selectively tosylating a diol of the formula ##STR13##to obtain a mono-tosolyate of the formula ##STR14##thereafter converting the mono-tosylate to an acetylenic compound having the formula ##STR15##catalytically hydrogenating the acetylenic bond to obtain a hydroxylated derivative of the formula ##STR16##and oxidizing the hydroxylated derivative to said ketone.