Sequential C−H Borylation and N-Demethylation of 1,1′-Biphenylamines: Alternative Route to Polycyclic BN-Heteroarenes

Jianbo Zhang; Hoimin Jung; Dongwook Kim; Sehoon Park; Sukbok Chang

doi:10.1002/anie.201902499

Sequential C−H Borylation and N-Demethylation of 1,1′-Biphenylamines: Alternative Route to Polycyclic BN-Heteroarenes

Jianbo Zhang, Hoimin Jung, Dongwook Kim, Sehoon Park^*, Sukbok Chang

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Described herein is an unprecedented access to BN-polyaromatic compounds from 1,1′-biphenylamines by sequential borane-mediated C(sp²)−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 PhSiH₃ to afford six-membered amine-borane adducts bearing a C(sp²)−B bond at the C2′-position. These species undergo an intramolecular N-demethylation with a B(C₆F₅)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.

Original language	English
Pages (from-to)	7361-7365
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	22
DOIs	https://doi.org/10.1002/anie.201902499
State	Published - 27 May 2019
Externally published	Yes

Keywords

C−H activation
boranes
heterocycles
isosterers
reaction mechanisms

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title = "Sequential C−H Borylation and N-Demethylation of 1,1′-Biphenylamines: Alternative Route to Polycyclic BN-Heteroarenes",

abstract = "Described herein is an unprecedented access to BN-polyaromatic compounds from 1,1′-biphenylamines by sequential borane-mediated C(sp2)−H borylation and intramolecular N-demethylation. The conveniently in situ generated Piers{\textquoteright} borane from a borinic acid reacts with a series of N,N-dimethyl-1,1′-biphenyl-2-amines in the presence of PhSiH3 to afford six-membered amine-borane adducts bearing a C(sp2)−B bond at the C2′-position. These species undergo an intramolecular N-demethylation with a B(C6F5)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.",

keywords = "C−H activation, boranes, heterocycles, isosterers, reaction mechanisms",

author = "Jianbo Zhang and Hoimin Jung and Dongwook Kim and Sehoon Park and Sukbok Chang",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = may,

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doi = "10.1002/anie.201902499",

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journal = "Angewandte Chemie - International Edition",

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T1 - Sequential C−H Borylation and N-Demethylation of 1,1′-Biphenylamines

T2 - Alternative Route to Polycyclic BN-Heteroarenes

AU - Zhang, Jianbo

AU - Jung, Hoimin

AU - Kim, Dongwook

AU - Park, Sehoon

AU - Chang, Sukbok

PY - 2019/5/27

Y1 - 2019/5/27

N2 - Described herein is an unprecedented access to BN-polyaromatic compounds from 1,1′-biphenylamines by sequential borane-mediated C(sp2)−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 PhSiH3 to afford six-membered amine-borane adducts bearing a C(sp2)−B bond at the C2′-position. These species undergo an intramolecular N-demethylation with a B(C6F5)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.

AB - Described herein is an unprecedented access to BN-polyaromatic compounds from 1,1′-biphenylamines by sequential borane-mediated C(sp2)−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 PhSiH3 to afford six-membered amine-borane adducts bearing a C(sp2)−B bond at the C2′-position. These species undergo an intramolecular N-demethylation with a B(C6F5)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.

KW - C−H activation

KW - boranes

KW - heterocycles

KW - isosterers

KW - reaction mechanisms

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U2 - 10.1002/anie.201902499

DO - 10.1002/anie.201902499

M3 - 文章

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AN - SCOPUS:85064670664

SN - 1433-7851

VL - 58

SP - 7361

EP - 7365

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 22

ER -

Sequential C−H Borylation and N-Demethylation of 1,1′-Biphenylamines: Alternative Route to Polycyclic BN-Heteroarenes

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Keywords

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