title: Benzannulation of triynes to generate functionalized arenes by spontaneous incorporation of nucleophiles.
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.
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA).
authors.forename: Rajdip
authors.initials: R
authors.lastname: Karmakar
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA).
authors.forename: Sang Young
authors.initials: SY
authors.lastname: Yun
authors.affiliation: College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China).
authors.forename: Jiajia
authors.initials: J
authors.lastname: Chen
authors.affiliation: College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China). xyz@wzu.edu.cn.
authors.forename: Yuanzhi
authors.initials: Y
authors.lastname: Xia
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA). dsunglee@uic.edu.
authors.forename: Daesung
authors.initials: D
authors.lastname: Lee
keywords: annulation; arenes; rearrangement; regioselectivity; ruthenium