We demonstrate that metal-catalyzed enantioselective benzylation reactions of allylic electrophiles can occur directly from aryl acetic acids. The reaction proceeds via a pathway in which decarboxylation is the terminal event, occurring after stereoselective carbon−carbon bond formation. This mechanistic feature enables enantioselective benzylation without the generation of a highly basic nucleophile. Thus, the process has broad functional group compatibility that would not be possible employing established protocols.

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.

Z-olefins are important functional units in synthetic chemistry;t heir 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.I nt his 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.

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