Details

Autor(en) / Beteiligte

• 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

Titel

Taming Chiral Quaternary Stereocenters via Remote H‐Bonding Stereoinduction in Palladium‐Catalyzed (3+2) Cycloadditions

Ist Teil von

• Angewandte Chemie International Edition, 2023-01, Vol.62 (3), p.e202212444-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

MEDLINE

Beschreibungen/Notizen

• 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. Two palladium‐catalyzed asymmetric (3+2) cycloadditions of donor‐acceptor (D‐A) cyclopropenes bearing two different electron‐withdrawing groups were reported. Various chiral five‐membered oxa‐ and aza‐heterocycles were produced, and good yields and high stereoselectivities were obtained. The key to the success of this reaction is the remote stereoinduction through H‐bonding from chiral ligands.