title: Rhodium-Catalyzed Intramolecular [5+2] Cycloaddition of Inverted 3-Acyloxy-1,4-enyne and Alkyne: Experimental and Theoretical Studies.
abstract: By switching the position of the alkene and alkyne, a new type of 3-acyloxy-1,4-enyne (ACE) five-carbon building block was developed for Rh-catalyzed intramolecular [5+2] cycloaddition. An electron-withdrawing acyl group on the alkyne termini of the ACE was essential for a regioselective 1,2-acyloxy migration. This new method provided bicyclic [5.3.0]decatrienes that are different from previous methods because of the positions of the alkenes and the acyloxy group. Multiple mechanistic pathways become possible for this new [5+2] cycloaddition and they are investigated by computational studies.
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison, Madison, WI 53705, USA.
authors.forename: Xiaoxun
authors.initials: X
authors.lastname: Li
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison, Madison, WI 53705, USA.
authors.forename: Wangze
authors.initials: W
authors.lastname: Song
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy, Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071, P. R. China.
authors.forename: Xiaona
authors.initials: X
authors.lastname: Ke
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy, Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071, P. R. China. xxfang@nankai.edu.cn.
authors.forename: Xiufang
authors.initials: X
authors.lastname: Xu
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA.
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison, Madison, WI 53705, USA.|School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou, 310023, P. R. China.
authors.forename: Xian-Liang
authors.initials: XL
authors.lastname: Zhao
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison, Madison, WI 53705, USA. weiping.tang@wisc.edu.|Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA. weiping.tang@wisc.edu.
authors.forename: Weiping
authors.initials: W
authors.lastname: Tang
keywords: catalysis; cycloaddition; enynes; rhodium; seven-membered rings