TY - JOUR
T1 - Elusive metal-free primary amination of arylboronic acids
T2 - Synthetic studies and mechanism by density functional theory
AU - Zhu, Chen
AU - Li, Gongqiang
AU - Ess, Daniel H.
AU - Falck, J R
AU - Kürti, László
N1 - Copyright:
Copyright 2013 Elsevier B.V., All rights reserved.
PY - 2012/11/7
Y1 - 2012/11/7
N2 - Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.
AB - Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.
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U2 - 10.1021/ja309637r
DO - 10.1021/ja309637r
M3 - Article
C2 - 23082853
AN - SCOPUS:84868578140
SN - 0002-7863
VL - 134
SP - 18253
EP - 18256
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -