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Sequential C−H Borylation and N‐Demethylation of 1,1′‐Biphenylamines: Alternative Route to Polycyclic BN‐Heteroarenes
Author(s) -
Zhang Jianbo,
Jung Hoimin,
Kim Dongwook,
Park Sehoon,
Chang Sukbok
Publication year - 2019
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.201902499
Subject(s) - borylation , chemistry , intramolecular force , borane , demethylation , amine gas treating , medicinal chemistry , ionic bonding , biphenyl , isoquinoline , stereochemistry , catalysis , organic chemistry , biochemistry , alkyl , gene expression , aryl , dna methylation , gene , ion
Described herein is an unprecedented access to BN‐polyaromatic compounds from 1,1′‐biphenylamines by sequential borane‐mediated C(sp 2 )−H borylation and intramolecular N‐demethylation. The conveniently in situ generated Piers’ borane from a borinic acid reacts with a series of N , N ‐dimethyl‐1,1′‐biphenyl‐2‐amines in the presence of PhSiH 3 to afford six‐membered amine‐borane adducts bearing a C(sp 2 )−B bond at the C2′‐position. These species undergo an intramolecular N‐demethylation with a B(C 6 F 5 ) 3 catalyst to provide BN‐isosteres of polyaromatics. According to computational studies, a stepwise ionic pathway is suggested. Photophysical characters of the resultant BN‐heteroarenes shown them to be distinctive from those of all‐carbon analogues.