Enantioselective Rhodium‐Catalyzed Cycloisomerization of (E)‐1,6‐Enynes |
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| Authors: | Dr Xu Deng Shao‐Fei Ni Zheng‐Yu Han Yu‐Qing Guan Prof?Dr Hui Lv Prof?Dr Li Dang Prof?Dr Xu‐Mu Zhang |
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| Institution: | 1. Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P.R. China;2. Department of Chemistry, South University of Science and Technology of China, Shenzhen, P.R. China |
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| Abstract: | An enantioselective rhodium(I)‐catalyzed cycloisomerization reaction of challenging (E)‐1,6‐enynes is reported. This novel process enables (E)‐1,6‐enynes with a wide range of functionalities, including nitrogen‐, oxygen‐, and carbon‐tethered (E)‐1,6‐enynes, to undergo cycloisomerization with excellent enantioselectivity, in a high‐yielding and operationally simple manner. Moreover, this RhI‐diphosphane catalytic system also exhibited superior reactivity and enantioselectivity for (Z)‐1,6‐enynes. A rationale for the striking reactivity difference between (E)‐ and (Z)‐1,6‐enynes using RhI‐BINAP and RhI‐TangPhos is outlined using DFT studies to provide the necessary insight for the design of new catalyst systems and the application to synthesis. |
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| Keywords: | (E)-1 6-enyne asymmetric synthesis cycloisomerization rhodium catalysis TangPhos |
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