Patent ID: 7230100

Claim:
A stereoselective process for making predominantly a cis compound of formula (A): wherein R1 is a base moiety selected from: X is oxygen, NH or sulfur; Y is oxygen, NH or sulfur; R8 and R9 are independently selected from hydrogen, hydroxyl, amino, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-10 acyl, C 6-10 aryl, C 6-11 carbonylaryl, C 1-7 carbonyloxyalkyl, C 6-11 carbonyloxyaryl, C 2-7 carbonylaminoalkyl, and amino acids; R8 can also be a saturated or unsaturated C 3-8 carbocyclic ring optionally substituted by COOH, C(O)NH 2 , OH, SH, NH, NO 2 , C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halogen, C(O)R14 or C(O)OR15, and R9H, C 1-6 alkyl, C 2-6 alkenyl or C 2-6 alkynyl; R8 and R9 can also together be connected to the nitrogen atom to form a saturated or unsaturated C 3-8 heterocyclic ring optionally substituted by C(O)OH, C(O)NH2, OH, SH, NH2, NO2, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halogen, C(O)R14—C 2-6 alkynyl or C(O)OR15; R14 is C 1-6 alkyl or C 2-6 alkenyl; R15 is C 1-6 alkyl, C 2-6 alkenyl, or C 2-6 alkynyl; and R10, R11, R12 and R13 are each independently selected from hydrogen, halogen, hydroxyl, amino, cyano, carboxyl, carbamoyl, C 2-7 alkoxycarbonyl, hydroxymethyl, trifluoromethy, C 6-10 arylthio, C 1-6 alkyl, C 2-6 alkeny substituted or unsubstituted with halogen or azido, C 2-6 alkynyl, C 1-6 acyloxy, thiocarboxy, thiocarbamoyl, carbamate, ureido, amidino, or C 6-10 aryloxy; and Q is carbon, oxygen or sulfur; said process comprising: coupling a compound of formula (B): wherein R2 is C 7-10 aralalkyl, C 1-16 acyl or Si(Z 1 )(Z 2 )(Z 3 ), and Z 1 , Z 2 and Z 3 independently selected from hydrogen; C 1-20 alkyl optionally substituted by fluoro, bromo, chloro, iodo, C 1-6 alkoxy or C 6-20 aryloxy; C 7-20 aralkyl optionally substituted by halogen, C 1-20 alkyl or C 1-20 alkoxy; C 6-20 aryl optionally substituted by fluoro, bromo, chloro, iodo, C 1-20 alkyl or C 1-20 alkoxy; trialkylsilyl; fluoro; bromo; chloro and iodo; with a base which yields R1 in a C 1-10 coupling solvent in the presence of a catalytic amount at least one ion selected from ions of the elements of group IB or IIB of the periodic table, a tertiary amine and a Lewis acid to yield an intermediate of formula (D): wherein R1, R2 and Q are defined above; and deprotecting the intermediate of formula (D) to yield the cis compound of formula (A).