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- Title
Taming Chiral Quaternary Stereocenters via Remote H‐Bonding Stereoinduction in Palladium‐Catalyzed (3+2) Cycloadditions.
- Authors
Xiao, Yu‐Qing; Li, Miao‐Miao; Zhou, Zheng‐Xin; Li, Yu‐Jie; Cao, Meng‐Yue; Liu, Xiao‐Peng; Lu, Hai‐Hua; Rao, Li; Lu, Liang‐Qiu; Beauchemin, André M.; Xiao, Wen‐Jing
- Abstract
Ring‐opening transformations of donor‐acceptor (D‐A) cyclopropanes enable the rapid assembly of complex molecules. However, the enantioselective formation of chiral quaternary stereocenters using substrates bearing two different acceptors remains a challenge. Herein, we describe the first palladium‐catalyzed highly diastereo‐ and enantioselective (3+2) cycloaddition of vinyl cyclopropanes bearing two different electron‐withdrawing groups, a subset of D‐A cyclopropanes. The key to the success of this reaction is the remote stereoinduction through hydrogen bond from chiral ligands, which thereby addressed the aforementioned challenge. A variety of chiral five‐membered heterocycles were produced in good yields and with high stereoselectivity (up to 99 % yields, 99 : 1 er and >19 : 1 dr). In‐depth mechanistic investigations, including control experiments and theoretical calculations, revealed the origin of the stereoselectivity and the importance of H‐bonding in stereocontrol.
- Subjects
RING formation (Chemistry); HYDROGEN bonding; STEREOSELECTIVE reactions; LIGANDS (Chemistry); HETEROCYCLIC compounds
- Publication
Angewandte Chemie, 2023, Vol 135, Issue 3, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202212444