Regio- and enantioselective umpolung gem-difluoroallylation of hydrazones via palladium catalysis enabled by N-heterocyclic carbene ligand

Shuai Huang, Fei-Fei Tong, Da-Chang Bai, Gao-Peng Zhang, Yang-Jie Jiang, Bo Zhang, Xuebing Leng, Ying-Long Guo, Xiao-Long Wan, Xingang Zhang (), Chang-Hua Ding () and Xue-Long Hou ()
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Shuai Huang: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Fei-Fei Tong: Center for Excellence in Molecular Synthesis, SIOC, CAS
Da-Chang Bai: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Gao-Peng Zhang: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Yang-Jie Jiang: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Bo Zhang: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Xuebing Leng: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Ying-Long Guo: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)
Xiao-Long Wan: Center for Excellence in Molecular Synthesis, SIOC, CAS
Xingang Zhang: Center for Excellence in Molecular Synthesis, SIOC, CAS
Chang-Hua Ding: Innovative Drug Research Center, Shanghai University
Xue-Long Hou: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS)

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract The enantioselective construction of C–CF2R (R: alkyl or fluoroalkyl) bonds has attracted the attention of synthetic chemists because of the importance of chiral fluorinated compounds in life and materials sciences. Catalytic asymmetric fluoroalkylation has mainly been realized under organocatalysis and Lewis acid catalysis, with substrates limited to carbonyl compounds. Few examples using transition-metal catalysis exist, owing to side reactions including decomposition and isomerization of fluoroalkylating reagents. Herein we report umpolung asymmetric difluoroallylation of hydrazones with 3-bromo-3,3-difluoropropene (BDFP) under palladium catalysis. Difluoroallylation products having quaternary chiral carbon centers are afforded in good yields with high α/γ- and enantioselectivities. The usefulness of the reaction products is demonstrated and an inner-sphere mechanism of the reaction is proposed. The use of chiral N-heterocyclic carbene as ligand is the key for the selectivities as well as the productivity of the reaction.

Date: 2021
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DOI: 10.1038/s41467-021-26667-0

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