Construction of Acyclic Quaternary Carbon Stereocenters via Enantioselective Nickel Catalysis

Abstract

The construction of acyclic quaternary carbon stereocenters, which are ubiquitous in many bioactive compounds, pharmaceuticals and natural products, has been a long persuit in synthetic organic chemistry. Among numerous methods, enantioselective nickel-catalysis has attracted incremental attention in recent years. This review summarizes the recent development in the asymmetric strategies, research progress, mechanistic investigations for the generation of acyclic quaternary carbon stereocenters via enantioselective nickel catalysis.

Key Scientists: In 2006, the Zhou group and RajanBabu group realized the nickel-catalyzed enantioselective hydrovinylation of α-substituted styrenes and ethylene to construct acyclic quaternary carbon stereocenters (QCSs) by using spiro- and binaphthyl phosphoramidite ligands, respectively. In 2016, Watson developed a nickel-catalyzed Suzuki-Miyaura arylation to generate acyclic QCSs via chirality transfer reaction. In 2017, the Feng and the Fu group developed nickel-catalyzed enantioselective conjugated/Michael additions to build acyclic QCSs, respectively. In 2020, the Fang group made the first success in the construction of QCSs by nickel-catalyzed hydrocyanation of alkenes and allenes. In 2021, Gregory C. Fu and co-workers disclosed a nickel-catalyzed enantioselective α-functionalization of carbonyl compounds that could form acyclic QCSs. At the same time, the Shi group constructed chiral acyclic QCSs via nickel-catalyzed functionalization of alkenes. In 2023, Kleij and co-workers applied a new strategy for Ni-catalyzed regio- and enantioselective homoallylic coupling to construct acyclic QCSs. In the same year, Tao and co-workers demonstrated a novel strategy that is dinickel-catalyzed enantioselective α-alkylation of carbonyl compounds with alkyl iodides.

Keywords

Nickel catalysis / Enantioselectivity / Alkenes / Acyclic / Quaternary carbon stereocenters / Asymmetric catalysis / Cross-coupling / Chirality

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2024 SIOC, CAS, Shanghai, & WILEY-VCH GmbH