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Selective [5,5]‐Sigmatropic Rearrangement by Assembly of Aryl Sulfoxides with Allyl Nitriles
Author(s) -
Zhang Lei,
He JiaNi,
Liang Yuchen,
Hu Mengjie,
Shang Li,
Huang Xin,
Kong Lichun,
Wang ZhiXiang,
Peng Bo
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201900434
Subject(s) - sigmatropic reaction , aryl , chemistry , combinatorial chemistry , stereochemistry , organic chemistry , alkyl
Aromatic [5,5]‐sigmatropic rearrangement is an appealing protocol for accessing 1,4‐substituted arenes. However, such a protocol has not been well utilized in organic synthesis because of the difficulties in the synthesis of the substrates, selectivity issues, and limited substrate scope. Described herein is a new [5,5]‐sigmatropic reaction utilizing readily available aryl sulfoxides and allyl nitriles. This reaction features mild reaction conditions, high chemo‐ and regioselectivity, excellent functional‐group compatibility, and broad substrate scope. Computational studies suggest that the success of the reaction can be attributed to the selective electrophilic assembly of the rearrangement precursors, in which a linear ‐C=C=N‐ linkage favors [5,5]‐sigmatropic rearrangement over the competitive [3,3]‐sigmatropic rearrangement.