Synthesis of α-Quaternary β-Lactams via Copper-Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross-Coupling with Organoboronate Esters

Wang，Fu Li1,2; Liu，Lin1,2; Yang，Chang Jiang1,2; Luan，Cheng2,3; Yang，Jing4; Chen，Ji Jun2; Gu，Qiang Shuai3; Li，Zhong Liang3; Liu，Xin Yuan2

2022

10.1002/anie.202214709

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Impact Factor & Quartile

1433-7851

1521-3773

The copper-catalyzed enantioconvergent radical C(sp)−C(sp) cross-coupling of tertiary α-bromo-β-lactams with organoboronate esters could provide the synthetically valuable α-quaternary β-lactams. The challenge arises mainly from the construction of sterically congested quaternary stereocenters between the tertiary alkyl radicals and chiral copper(II) species. Herein, we describe our success in achieving such transformations through the utilization of a copper/hemilabile N,N,N-ligand catalyst to forge the sterically congested chiral C(sp)−C(sp) bond via a single-electron reduction/transmetalation/bond formation catalytic cycle. The synthetic potential of this approach is shown in the straightforward conversion of the corresponding products into many valuable building blocks. We hope that the developed catalytic cycle would open up new vistas for more enantioconvergent cross-coupling reactions.

Asymmetric Catalysis Copper Cross-Coupling Radical Chemistry β-Lactam

SCI

English

NI Journal Papers

Others

National Key R&D Program of China["2021YFF0701604","2021YFF0701704"] ; National Natural Science Foundation of China["22025103","21831002","21901106","22001109","22201127","22271133","22101186","22101122"] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Special Funds[JCYJ20200109141001789] ; Shenzhen Science and Technology Program[KQTD20210811090112004]

Chemistry

Chemistry, Multidisciplinary

WOS:000918794700001

WILEY-V C H VERLAG GMBH

CHEMISTRY

2-s2.0-85143273018

Scopus

1.School of Science and Institute of Scientific Research,Great Bay University,Dongguan,523000,China
2.Shenzhen Grubbs Institute and Department of Chemistry,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518055,China
3.Academy for Advanced Interdisciplinary Studies and Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
4.College of Health Science and Environmental Engineering,Shenzhen Technology University,Shenzhen,518118,China

Wang，Fu Li,Liu，Lin,Yang，Chang Jiang,et al. Synthesis of α-Quaternary β-Lactams via Copper-Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross-Coupling with Organoboronate Esters[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2022.

Wang，Fu Li.,Liu，Lin.,Yang，Chang Jiang.,Luan，Cheng.,Yang，Jing.,...&Liu，Xin Yuan.(2022).Synthesis of α-Quaternary β-Lactams via Copper-Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross-Coupling with Organoboronate Esters.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.

Wang，Fu Li,et al."Synthesis of α-Quaternary β-Lactams via Copper-Catalyzed Enantioconvergent Radical C(sp3)−C(sp2) Cross-Coupling with Organoboronate Esters".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022).