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Proximal and Remote Hydrocarboxylation of Alkenes with Carbon Dioxide Enabled by Nickel-Catalyzed Hydrogen Atom
Rong-De He1, Yixin Lu1,2
1Department of Chemistry, National University of Singapore, Singapore, 117543, Singapore.
Abstract:
The utilization of carbon dioxide and alkenes as feedstocks for the synthesis of carboxylic acids holds great significance in the realm of sustainable chemistry. Nonetheless, achieving selective C─H bond carboxylation of alkenes with broad applicability has long been a challenging task. Herein, we present a straightforward and unifying approach for the preparation of α-carboxylic acids through nickel-catalyzed radical hydrocarboxylation of both functionalized and unactivated, simple alkenes, at proximal and remote sites. Notably, this operationally simple catalytic reaction exhibits a broad substrate scope, having excellent regio- and chemoselectivities, and is suitable for late-stage carboxylation of bioactive molecules. Preliminary mechanistic investigations showed that a nickel-catalyzed hydrogen atom transfer (Ni-HAT) pathway is in operation, accounting for the site-selective hydrocarboxylation protocol for various alkene substrates.
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