Spectroscopic studies of the Chan-Lam amination: a mechanism-inspired solution to boronic ester reactivity

Julien C. Vantourout, Haralampos N. Miras, Albert Isidro-Llobet, Stephen Sproules, Allan J. B. Watson

Research output: Contribution to journalArticle

83 Citations (Scopus)

Abstract

We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, in-cluding off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxida-tion/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I)→Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.
LanguageEnglish
Pages4769–4779
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number13
DOIs
Publication statusPublished - 7 Mar 2017

Fingerprint

Amination
Amines
Esters
Crystallography
Boric acid
Spectrum Analysis
Spectroscopy
Oxidation
boric acid

Keywords

  • Chan-Lam amination reaction
  • spectroscopy
  • computational modeling
  • crystallography
  • off-cycle inhibitory processes
  • amines
  • organoboron reactivity issues
  • oxidation/protodeboronation side reactions

Cite this

Vantourout, Julien C. ; Miras, Haralampos N. ; Isidro-Llobet, Albert ; Sproules, Stephen ; Watson, Allan J. B. / Spectroscopic studies of the Chan-Lam amination : a mechanism-inspired solution to boronic ester reactivity. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 13. pp. 4769–4779.
@article{2ab363b89799484880b19fa1257fb18f,
title = "Spectroscopic studies of the Chan-Lam amination: a mechanism-inspired solution to boronic ester reactivity",
abstract = "We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, in-cluding off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxida-tion/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I)→Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.",
keywords = "Chan-Lam amination reaction, spectroscopy, computational modeling, crystallography, off-cycle inhibitory processes, amines, organoboron reactivity issues, oxidation/protodeboronation side reactions",
author = "Vantourout, {Julien C.} and Miras, {Haralampos N.} and Albert Isidro-Llobet and Stephen Sproules and Watson, {Allan J. B.}",
note = "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright {\circledC} American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.6b12800.",
year = "2017",
month = "3",
day = "7",
doi = "10.1021/jacs.6b12800",
language = "English",
volume = "139",
pages = "4769–4779",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "13",

}

Spectroscopic studies of the Chan-Lam amination : a mechanism-inspired solution to boronic ester reactivity. / Vantourout, Julien C.; Miras, Haralampos N.; Isidro-Llobet, Albert; Sproules, Stephen; Watson, Allan J. B.

In: Journal of the American Chemical Society, Vol. 139, No. 13, 07.03.2017, p. 4769–4779.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Spectroscopic studies of the Chan-Lam amination

T2 - Journal of the American Chemical Society

AU - Vantourout, Julien C.

AU - Miras, Haralampos N.

AU - Isidro-Llobet, Albert

AU - Sproules, Stephen

AU - Watson, Allan J. B.

N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.6b12800.

PY - 2017/3/7

Y1 - 2017/3/7

N2 - We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, in-cluding off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxida-tion/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I)→Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.

AB - We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, in-cluding off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxida-tion/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I)→Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.

KW - Chan-Lam amination reaction

KW - spectroscopy

KW - computational modeling

KW - crystallography

KW - off-cycle inhibitory processes

KW - amines

KW - organoboron reactivity issues

KW - oxidation/protodeboronation side reactions

UR - http://pubs.acs.org/doi/abs/10.1021/jacs.6b12800

U2 - 10.1021/jacs.6b12800

DO - 10.1021/jacs.6b12800

M3 - Article

VL - 139

SP - 4769

EP - 4779

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 13

ER -