Catalytic Z-Selective Olefin Cross-Metathesis

Significance

Selective formation of Z-disubstituted alkenes is an important synthetic problem, which is nonetheless poorly explored. In this ­paper, the authors developed molybdenum-­mediated scalable Z-selective cross-metathesis protocols, involving terminal enol ethers (never ­reported in cross-metathesis so far) and allylic amides (previously known to provide E-selectivity only). The synthetic utility of the developed methodologies was exemplified by implementation thereof in the total syntheses of biologically im­portant products C18 (plasm)-16:0 (PC) and KRN7000. The paper provides detailed considerations of mechanistic details and methodological challenges associated with them.