TY - JOUR
T1 - Dirhodium-catalyzed C-H arene amination using hydroxylamines
AU - Paudyal, Mahesh P.
AU - Adebesin, Adeniyi Michael
AU - Burt, Scott R.
AU - Ess, Daniel H.
AU - Ma, Zhiwei
AU - Kürti, László
AU - Falck, J R
N1 - Funding Information:
J.R.F. thanks NIH (grant HL034300, HL111392, DK038226) and the Robert A. Welch Foundation (grant I-0011) for funding. L.K. gratefully acknowledges the generous financial support of Rice University, NIH (grant R01 GM-114609-01), NSF (CAREER:SusChEM CHE-1455335), the Robert A. Welch Foundation (grant C-1764), American Chemical Society Petroleum Research Fund (grant 51707-DNI1), Amgen (2014 Young Investigators' Award to L.K.), and Biotage (2015 Young Principal Investigator Award). A provisional patent application (patent no. 62/360,859) has been submitted and assigned jointly to University of Texas Southwestern and Rice University.
Publisher Copyright:
Copyright © 2016 by the American Association for the Advancement of Science; all rights reserved.
PY - 2016/9/9
Y1 - 2016/9/9
N2 - Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals, and functional materials, as well as in bioactive natural products. However, there is a dearth of generally applicablemethods for the direct replacement of aryl hydrogens with NH2/NH(alkyl) moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using NH2/NH(alkyl)-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.
AB - Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals, and functional materials, as well as in bioactive natural products. However, there is a dearth of generally applicablemethods for the direct replacement of aryl hydrogens with NH2/NH(alkyl) moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using NH2/NH(alkyl)-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.
UR - http://www.scopus.com/inward/record.url?scp=84987729357&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84987729357&partnerID=8YFLogxK
U2 - 10.1126/science.aaf8713
DO - 10.1126/science.aaf8713
M3 - Article
C2 - 27609890
AN - SCOPUS:84987729357
SN - 0036-8075
VL - 353
SP - 1144
EP - 1147
JO - Science
JF - Science
IS - 6304
ER -