Enantioselective Rhodium-Catalyzed Cycloisomerization of (E)-1,6-Enynes

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 excelle...

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Published in:Angewandte Chemie (International ed.) 2016-05, Vol.55 (21), p.6295-6299
Main Authors: Deng, Xu, Ni, Shao-Fei, Han, Zheng-Yu, Guan, Yu-Qing, Lv, Hui, Dang, Li, Zhang, Xu-Mu
Format: Article
Language:English
Subjects:
(E)-1
(E)-1,6-enyne
6-enyne
asymmetric synthesis
Catalysis
Chemical synthesis
cycloisomerization
Enantiomers
Isomerization
Rhodium
rhodium catalysis
TangPhos
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Summary: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. A solution after 15 years: The first rhodium(I)‐catalyzed asymmetric cycloisomerization reaction of challenging (E)‐configured 1,6‐enyes is reported. The reaction provides access to five‐membered carbo‐ and heterocycles with excellent enantioselectivity. DFT studies provide a rationale for the striking reactivity difference between (E)‐ and (Z)‐1,6‐enynes using RhI‐BINAP and RhI‐TangPhos.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201601061