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Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification
Author(s) -
Wang Guoqiang,
Zhang Honglin,
Zhao Jiyang,
Li Wei,
Cao Jia,
Zhu Chengjian,
Li Shuhua
Publication year - 2016
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.201511917
Subject(s) - diborane , chemistry , pyridine , homolysis , catalysis , boron , bond cleavage , deoxygenation , density functional theory , radical , computational chemistry , combinatorial chemistry , medicinal chemistry , organic chemistry
Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B−B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B 2 (pin) 2 at mild conditions.