Chemoselective Synthesis of Z ‐Olefins through Rh‐Catalyzed Formate‐Mediated 1,6‐Reduction

Z ‐olefins are important functional units in synthetic chemistry; their preparation has thus received considerable attention. Many prevailing methods for cis ‐olefination are complicated by the presence of multiple unsaturated units or electrophilic functional groups. In this study, Z ‐olefins are delivered through selective reduction of activated dienes using formic acid. The reaction proceeds with high regio‐ and stereoselectivity (typically >90:10 and >95:5, respectively) and preserves other alkenyl, alkynyl, protic, and electrophilic groups.