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Enantioselective Rhodium‐Catalyzed Cycloisomerization of ( E )‐1,6‐Enynes
Author(s) -
Deng Xu,
Ni ShaoFei,
Han ZhengYu,
Guan YuQing,
Lv Hui,
Dang Li,
Zhang XuMu
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601061
Subject(s) - cycloisomerization , rhodium , enantioselective synthesis , reactivity (psychology) , catalysis , chemistry , combinatorial chemistry , organic chemistry , medicine , alternative medicine , pathology
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 Rh I ‐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 Rh I ‐BINAP and Rh I ‐TangPhos is outlined using DFT studies to provide the necessary insight for the design of new catalyst systems and the application to synthesis.