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Enantioselective Preparation of Arenes with β-Stereogenic Centers: Confronting the 1,1-Disubstituted Olefin Problem Using CuH/Pd Cooperative Catalysis.

ABSTRACT: Arenes with β-stereogenic centers are important substructures in pharmaceuticals and natural products. We have developed an asymmetric anti-Markovnikov hydroarylation of 1,1-disubstituted olefins by dual palladium and copper hydride catalysis as a convenient and general approach to access these substructures. This efficient one-step process addresses several limitations of the traditional stepwise approaches. The use of cesium benzoate as a base and a common phosphine ligand for both the Cu- and Pd-catalyzed processes were important discoveries that allow these challenging olefin substrates to be efficiently transformed. A variety of aryl bromide coupling partners, including numerous heterocycles, were coupled with 1,1-disubstituted alkenes to generate arenes with β-stereogenic centers.

SUBMITTER: Lu Z

PROVIDER: S-EPMC8146278 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Enantioselective Preparation of Arenes with β-Stereogenic Centers: Confronting the 1,1-Disubstituted Olefin Problem Using CuH/Pd Cooperative Catalysis.

Lu Zhaohong Z Buchwald Stephen L SL

Angewandte Chemie (International ed. in English) 20200630 37

Arenes with β-stereogenic centers are important substructures in pharmaceuticals and natural products. We have developed an asymmetric anti-Markovnikov hydroarylation of 1,1-disubstituted olefins by dual palladium and copper hydride catalysis as a convenient and general approach to access these substructures. This efficient one-step process addresses several limitations of the traditional stepwise approaches. The use of cesium benzoate as a base and a common phosphine ligand for both the Cu- and ...[more]

PMID: 32438497

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