TY - JOUR
T1 - Experimental and Theoretical Studies on Iron-Promoted Oxidative Annulation of Arylglyoxal with Alkyne
T2 - Unusual Addition and Migration on the Aryl Ring
AU - Hung, Chen Hsun
AU - Gandeepan, Parthasarathy
AU - Cheng, Lin Chieh
AU - Chen, Liang Yu
AU - Cheng, Mu Jeng
AU - Cheng, Chien Hong
N1 - Funding Information:
C.-H.H., P.G., L.-C.C., and C.-H.C. thank the Ministry of Science and Technology of the Republic of China (MOST-105-2633-M-007-003) for support of this research, the National Center for High-Performance Computing (account number: u32chc04) of Taiwan for providing computing time, and the Center for Advanced Instrumentation at National Chiao Tung University and National Cheng Kung University for mass spectrometry analysis. M.-J.C. acknowledges the financial support from the Ministry of Science and Technology of the Republic of China, under grant no. MOST 105-2113-M-006-017-MY2.
Funding Information:
C.-H.H. P.G., L.-C.C., and C.-H.C. thank the Ministry of Science and Technology of the Republic of China (MOST-105-2633-M-007-003) for support of this research, the National Center for High-Performance Computing (account number: u32chc04) of Taiwan for providing computing time, and the Center for Advanced Instrumentation at National Chiao Tung University and National Cheng Kung University for mass spectrometry analysis. M.-J.C. acknowledges the financial support from the Ministry of Science and Technology of the Republic of China, under grant no. MOST 105-2113-M-006-017-MY2.
Publisher Copyright:
© 2017 American Chemical Society.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2017/11/29
Y1 - 2017/11/29
N2 - An Fe(III)-promoted oxidative annulation reaction was developed for the synthesis of 1,2-naphthoquinones. A variety of substituted arylglyoxals and internal alkynes undergo the transformation in the presence of FeCl3 at room temperature to afford the 1,2-naphthoquinone products in good yields in a short reaction time. Interestingly, the products show unusual pseudomigration of the substituent on the arene ring of arylglyoxals. A possible mechanism involving Fe(III)-promoted formation of a vinyl cation from arylglyoxal and alkyne, electrophilic addition of the vinyl cation to the ipso carbon of the aryl group to give a spiral intermediate, and then migration of the keto carbon to the ortho carbon was proposed as key steps and verified using quantum mechanics.
AB - An Fe(III)-promoted oxidative annulation reaction was developed for the synthesis of 1,2-naphthoquinones. A variety of substituted arylglyoxals and internal alkynes undergo the transformation in the presence of FeCl3 at room temperature to afford the 1,2-naphthoquinone products in good yields in a short reaction time. Interestingly, the products show unusual pseudomigration of the substituent on the arene ring of arylglyoxals. A possible mechanism involving Fe(III)-promoted formation of a vinyl cation from arylglyoxal and alkyne, electrophilic addition of the vinyl cation to the ipso carbon of the aryl group to give a spiral intermediate, and then migration of the keto carbon to the ortho carbon was proposed as key steps and verified using quantum mechanics.
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U2 - 10.1021/jacs.7b05981
DO - 10.1021/jacs.7b05981
M3 - Article
C2 - 29088912
AN - SCOPUS:85035775543
SN - 0002-7863
VL - 139
SP - 17015
EP - 17021
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -