Rhodium‐Catalyzed Intramolecular [5+2] Cycloaddition of Inverted 3‐Acyloxy‐1,4‐enyne and Alkyne: Experimental and Theoretical Studies |
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| Authors: | Dr Xiaoxun Li Wangze Song Xiaona Ke Prof?Dr Xiufang Xu Prof?Dr Peng Liu Prof?Dr K N Houk Dr Xian‐liang Zhao Prof?Dr Weiping Tang |
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| Institution: | 1. School of Pharmacy, University of Wisconsin-Madison, Madison, USA;2. Department of Chemistry, Key Laboratory of Advanced Energy, Materials Chemistry (Ministry of Education), Nankai University, Tianjin, P. R. China;3. Department of Chemistry, University of Pittsburgh, Pittsburgh, USA;4. Department of Chemistry and Biochemistry, University of California, Los Angeles, USA;5. School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, Hangzhou, P. R. China;6. Department of Chemistry, University of Wisconsin-Madison, Madison, USA |
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| 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. |
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| Keywords: | catalysis cycloaddition enynes rhodium seven-membered rings |
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