Catalytic asymmetric carbon–carbon bond formation using alkenes as alkylmetal equivalents

Abstract

Catalytic asymmetric conjugate addition reactions with organometallic reagents are powerful reactions in synthetic chemistry. Procedures that use non-stabilized carbanions have been developed extensively, but these suffer from a number of limitations that prevent their use in many situations. Here, we report that alkylmetal species generated in situ from alkenes can be used in highly enantioselective 1,4-addition initiated by a copper catalyst. Using alkenes as starting materials is desirable because they are readily available and have favourable properties when compared to pre-made organometallics. High levels of enantioselectivity are observed at room temperature in a range of solvents, and the reaction tolerates functional groups that are not compatible with comparable methods—a necessary prerequisite for efficient and protecting-group-free strategies for synthesis. Organometallic reagents are widely used as nucleophiles in asymmetric catalysis. Here, alkylmetal species generated in situ by hydrometallation of alkenes are used in enantioselective copper-catalysed C–C bond formation. The process is formally an asymmetric reductive coupling of an alkene to an enone, and tolerates many functional groups.

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Maksymowicz, R., Roth, P. & Fletcher, S. Catalytic asymmetric carbon–carbon bond formation using alkenes as alkylmetal equivalents. Nature Chem 4, 649–654 (2012). https://doi.org/10.1038/nchem.1394

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