Benzannulation of Triynes to Generate Functionalized Arenes by Spontaneous Incorporation of Nucleophiles†
Rajdip Karmakar
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorDr. Sang Young Yun
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorJiajia Chen
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Yuanzhi Xia
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Yuanzhi Xia, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Daesung Lee, Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorCorresponding Author
Prof. Daesung Lee
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Yuanzhi Xia, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Daesung Lee, Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorRajdip Karmakar
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorDr. Sang Young Yun
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorJiajia Chen
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Yuanzhi Xia
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Yuanzhi Xia, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Daesung Lee, Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorCorresponding Author
Prof. Daesung Lee
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Yuanzhi Xia, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China)
Daesung Lee, Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607 (USA)
Search for more papers by this authorWe thank UIC (LAS-AFS, DL), NSF (CHE-1361620, DL), TACOMA Technology (DL), the Zhejiang Provincial NSF (LY13B020007, YX), and the NNSFC (21372178, YX) for financial support. We thank Prof. Neal Mankad for his help in obtaining X-ray structures. All computations were carried out on the High Performance Computation Platform of Wenzhou University. The mass spectrometry facility at UIUC is greatly acknowledged.
Graphical Abstract
Small but profound: In the benzannulation reaction of 1,3,8-triynes, a small structural difference has a profound impact on the structure of the products. When R is a silyl group, a nucleophile is incorporated into the newly formed benzene core, whereas when R is an aryl group, nucleophile trapping occurs at the benzylic carbon atom connected to the aryl group.
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.
Supporting Information
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