Enantioselective Rhodium‐Catalyzed Cycloisomerization of (E)‐1, 6‐Enynes. Issue 21 (9th April 2016)

• Record Type: Journal Article
• Authors: Deng, Xu; Ni, Shao‐Fei; Han, Zheng‐Yu; Guan, Yu‐Qing; Lv, Hui; Dang, Li; Zhang, Xu‐Mu
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 21(2016)
• Page Start: 6295
• Page End: 6299
• Publication Date: 2016-04-09
• Subjects: (E)-1, 6-enyne -- asymmetric synthesis -- cycloisomerization -- rhodium catalysis -- TangPhos; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601061
• Languages: English
• ISSNs: 1433-7851

Abstract

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 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. Abstract : 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 Rh I ‐BINAP and Rh I ‐TangPhos.