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Experimental and Computational Studies of the Iron‐Catalyzed Selective and Controllable Defluorosilylation of Unactivated Aliphatic gem ‐Difluoroalkenes
Author(s) -
Zhang Huan,
Wang Enhui,
Geng Shasha,
Liu Zhengli,
He Yun,
Peng Qian,
Feng Zhang
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100049
Subject(s) - silylation , stereoselectivity , catalysis , reactivity (psychology) , chemistry , nucleophile , combinatorial chemistry , functional group , compatibility (geochemistry) , organic chemistry , computational chemistry , materials science , medicine , polymer , alternative medicine , pathology , composite material
The first iron‐catalyzed defluorosilylation of unactivated gem‐difluoroalkenes was developed, delivering gem‐disilylated alkenes and (E)‐silylated alkenes with excellent efficiency. This protocol features good functional group compatibility and excellent regio‐ and stereoselectivity, enabling the late‐stage silylation of biologically relevant compounds, thus providing good opportunities for applications in medicinal chemistry. Preliminary mechanistic studies and DFT calculations reveal that a nucleophilic addition and elimination of the second C−F bond might be involved in the disilylation catalytic system, demonstrating unusual reactivity characteristics of iron catalysis.