Abstract
Saturated stereogenic centers containing C(sp3)–C(sp3) bonds comprise a major portion of organic molecules. Over the past decades, transition-metal-catalyzed
asymmetric C(sp3)–C(sp3) cross-coupling has evolved into an efficient strategy for constructing such stereogenic
centers. However, reaction modes to build asymmetric C(sp3)–C(sp3) bonds remain limited. Herein, a nickel-catalyzed enantioselective cross-hydrodimerization
between distinct alkenes to enable the enantioselective construction of alkyl–alkyl
bonds has been developed. In this reaction mode, N-acyl enamines (enamides) and unactivated alkenes undergo oxidative enantioselective
cross-hydrodimerization with excellent levels of chemo- and head-to-tail regioselectivity
to give enantioenriched N-acyl α-branched amines by forging the C(sp3)–C(sp3) bond with control of the enantioselectivity. The presence of both reducing and oxidizing
reagents in the reaction allows the use of alkenes as sole precursors to forge enantioselective
C(sp3)–C(sp3) bonds, representing a new reaction mode for asymmetric alkyl–alkyl cross-coupling.
The asymmetric cross-hydrodimerization between distinct alkenes provides a new strategy
for constructing saturated stereogenic centers containing C(sp3)–C(sp3) bonds.
Key words
asymmetric hydrodimerization of alkenes - asymmetric alkyl–alkyl coupling - nickel
catalysis - saturated stereogenic centers - alkyl electrophile free