A light-induced
redox-neutral Ni-catalyzed sp3 C–H
alkylation of unactivated alkenes with alkyl bromides possessing β-hydrogens
is described herein. The method is distinguished by its simplicity,
wide scope, and exquisite regio- and chemoselectivity profile, thus
offering an entry point to forge sp3–sp3 architectures.
We report a polystyrene-incorporated chiral nickel(II)-bisdiamine complex, which is accessible on gram-scale. This metal complex functions as a heterogeneous catalyst for the enantioselective Michael addition between malonates and aliphatic nitroalkenes, and it provides yields and enantioselectivities on par with homogeneous catalysts. Good functional group tolerance is reported for this reaction. Upon recycling, the catalyst achieves significantly higher TONs than previously reported. We demonstrate scalability to multigram-scale, compatibility with continuous flow production (4.43 gram), and application to the synthesis of the blockbuster drug Pregabalin. Finally, a new tandem reaction is disclosed.
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We report a simple method for copper-catalyzed benzylic C–H alkynylation that uses alkynylboronic esters as nucleophilic coupling partners. The catalytic system is readily available and the reaction takes place under mild conditions. Different substrates for the C–H functionalization, as well as various alkynylboronic ester nucleophiles, were evaluated. Finally, three examples of enantioselective C–H alkynylations are presented.
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