Diastereocontrolled synthesis of cis-olefins by selective C–C bond formation between alkyl and alkynyl groups coordinated to “Ir(CH
CHPPh3)(CO)(PPh3)2Ӡ
Abstract
CHCH3)2, cis-DPB) and
CHCH3)3, cis-TPB) are obtained in high yields by reactions of di- and tri-nuclear
C–Ir(CH3)(CH
CHPPh3)(CO)(PPh3)2)2]2+1 and [m,m-C6H3(C
C–Ir(CH3)(CH
CHPPh3)(CO)(PPh3)2)3]3+3 with HCl. The reaction of the mono-nuclear alkyl–
CHPPh3)(C
C-p-C6H4CH3)(CO)(PPh3)2]+7a with DCl selectively gives cis-CD3CD
CD(p-C6H4CH3)
8a-d5 while two isomers, cis-C6H5CD2CD
CD(p-C6H4CH3)
8b-d4 and cis-C6H5CD
CDCD2(p-C6H4CH3)
8b′-d4 are obtained from the reaction of [Ir(CH2Ph)(CH
CHPPh3)(C
C-p-C6H4CH3)(CO)(PPh3)2]+7b with DCl. Plausible reaction pathways containing the initial attack of H+ on the β-carbon of the alkynyl