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( o ‐Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors
Author(s) -
Suzuki Kensuke,
Nishimoto Yoshihiro,
Yasuda Makoto
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004692
Subject(s) - chemistry , borylation , alkyl , radical , homolysis , reactivity (psychology) , medicinal chemistry , photochemistry , xanthone , radical cyclization , radical nucleophilic aromatic substitution , reagent , aryl radical , stereochemistry , organic chemistry , nucleophilic substitution , aryl , nucleophilic aromatic substitution , medicine , alternative medicine , pathology
( o ‐Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and decarboxylative borylations proceeded in the presence of a radical initiator to give the corresponding organic boron compounds. Radical clock experiments and computational studies have provided insights into the mechanism of the homolytic substitution (S H 2) of the borylstannanes with alkyl radical intermediates. DFT calculation disclosed that the phenylenediamino structure lowered the LUMO level including the vacant p‐orbital on the boron atom to enhance the reactivity to alkyl radicals in S H 2. Moreover, C(sp 3 )‐H borylation of THF was accomplished using the triplet state of xanthone.