Stannane synthesis of prostanoids

A method for preparing 3-carba prostanoids of formula (III):

• wherein,
• X is O, CH2, C═O, or CH—OR4 in either configuration, or CH-halogen (F, Cl, Br, I) in either configuration;
• A is CH2;
• Q is H or C1-4 alkyl;
• R3 is H and one of:
• OR4, halogen, H, in either configuration, or, R3 is O;
• R4 is H, alkyl, acyl, or Si(R6)3, wherein R6 is independently C1-4 alkyl or phenyl;
• with the proviso that if R3 is O then X is not CH-halogen, and that if R3 is CH-halogen then X is not C═O;
• ω is
• wherein:
• ---- is an optional bond;
• D is H and one of:
• H, F or OR4, in either configuration;
• or D is O;
• X′ is (CH2)m or (CH2)mO, wherein m is 1 to 6;
• or X′ is CH—OH;
• and
• Y is a phenyl ring optionally substituted with alkyl, halo, trihalomethyl, alkoxy, acyl, acyloxy, amino, alkylamino, acylamino, or hydroxy;
• or Y is C1-6 alkyl or C3-8 cycloalkyl, optionally substituted with C1-6 alkyl, or
• X′—Y is (CH2)pY′;
• wherein p is 0 to 6;
• and
• wherein:
• W is CH2, O, S(O)q, NR5, CH2CH2, CH═CH, CH2O, CH2S(O)q, CH═N, or CH2NR5;
• wherein q is 0 to 2, and R5 is H, alkyl, or acyl;
• Z is H, alkyl, alkoxy, acyl, acyloxy, halo, trihalomethyl, amino, alkylamino, acylamino, or hydroxy;
• and
• ---- is an optional bond;
• or
• X1—Y is C1-6 alkyl, or C3-8 cycloalkyl, comprising the steps of:
• (a) reacting a compound of formula (VIII):
• wherein, R11 is C1-6 alkyl and Z1 is CH2OR1, CH(O-alkyl)2 or C(O-alkyl)3, and R1 is alkyl, arylalkyl, alkoxyalkyl or substituted silyl, with a compound of formula (V):
• R2CuLi.LiCN (V)
• wherein R is C1-6 alkyl, to form a product of formula (IX):
• (b) reacting the product (IX) with a compound of the formula (VII):
• to form a compound of formula (III), wherein A is CH2.