Patent ID: 6313341
Filing Date: 2001-11-06
Classification: C07C

Abstract:
Process for preparing prostaglandins shown by the formula (I) ##STR18##(wherein A is ethylene or (Z)-vinylene, X is CH.sub.2 OR.sup.2 or CO.sub.2 R.sup.2, R.sup.2 is an alkyl group of the carbon number of 1-5, H or a protecting group, R.omega.(OH) is a straight chain or branch chain alkyl group of the carbon number of 4-10 having a secondary or tertiary hydroxyl group, the steric configuration of hydroxyl group is R, S or a mixture of R and S, the steric configuration of branched chain alkyl group is R, S or a mixture of R and S, the stereochemistry of the formula (I) represents a relative steric configuration, and does not restrict an optically active substance or a racemic substance), comprising the steps, wherein(a) a hydroxy-1-alkyne shown by the formula (II) ##STR19##R.omega.(OH) has a same meaning as described above) is reacted with a tin hydride shown by the formula (III)(R.sup.3).sub.3 SnH (III)(wherein R .sup.3 is a lower alkyl group of the carbon number of 1-6, phenyl or cyclohexyl) to prepare subsequently (E,Z)-hydroxyvinylstannanes shown by the formula (IV) ##STR20##(wherein R.sup.3 and R.omega.(OH) have a same meaning as described above),(b) the (E)-substance and the (Z)-substance of (E, Z)-hydroxyvinylstannane compound are separated to prepare an (E)-hydroxyvinylstannane shown by the formula (V) ##STR21##(wherein R.sup.3 and R.omega.(OH) have a same meaning as described above),(c) a copper (I) salt shown by CuY (Y is --CN, --SCN or --OSO.sub.2 CF.sub.3) and an alkyllithium reagent shown by R.sup.4 Li (R.sup.4 is a lower alkyl) are added, orCuY (Y has a same meaning as described before), R.sup.4 Li (R.sup.4 has a same meaning as described before) and Lewis acid are added, orCuY (Y has a same meaning as described before), R.sup.4 Li (R.sup.4 has a same meaning as described before), Lewis acid and a lithium salt shown by LiZ (Z is a halogen atom or --OSO.sub.2 CF.sub.3) are added,to give a vinylcopper complex shown by the formula (VI) ##STR22##(wherein M is a reactive copper part having Y and Li, or a reactive copper part having Y, Li and Lewis acid, or a reactive copper part having Y, Li, Lewis acid and LiZ, R.omega.(OLi) represents a group in which hydrogen of the hydroxyl group in R.omega.(OH) is exchanged by Li),(d) a conjugate addition to an .alpha., .beta.-unsaturated cyclopentenone of the formula (VII) ##STR23##(wherein R.sup.1 is a protecting group, A and X have a same meaning as described before, and the formula (VII) does not restrict an optically active form or a racemic form) is carried out to prepare an intermediate of prostaglandins shown by the formula (VIII) ##STR24##(wherein R.sup.1, A, X and R.omega.(OH) have a same meaning as described before, and the stereochemistry of the formula (VIII) represents a relative steric configuration, and does not restrict an optically active form or a racemic form), and(e) the intermediate of prostaglandins shown by the formula (VIII) is treated with acid to carry out, the deprotection reaction.