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Benzannulation of Triynes to Generate Functionalized Arenes by Spontaneous Incorporation of Nucleophiles
Author(s) -
Karmakar Rajdip,
Yun Sang Young,
Chen Jiajia,
Xia Yuanzhi,
Lee Daesung
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201412468
Subject(s) - allene , chemistry , enyne , nucleophile , substituent , aromatization , aryl , moiety , alkyne , pericyclic reaction , stereochemistry , medicinal chemistry , organic chemistry , catalysis , alkyl
Abstract The thermal reaction of ester‐tethered 1,3,8‐triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene‐enyne intermediate generated by an Alder‐ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene‐enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane‐substituted 1,3,8‐triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene‐enyne intermediates.