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Utilizing Vinylcyclopropane Reactivity: Palladium‐Catalyzed Asymmetric [5+2] Dipolar Cycloadditions
Author(s) -
Li MiaoMiao,
Xiong Qin,
Qu BaoLe,
Xiao YuQing,
Lan Yu,
Lu LiangQiu,
Xiao WenJing
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006366
Subject(s) - reactivity (psychology) , palladium , cycloaddition , chemistry , catalysis , 1,3 dipolar cycloaddition , dipole , combinatorial chemistry , transition metal , computational chemistry , organic chemistry , medicine , alternative medicine , pathology
Vinylcyclopropanes (VCPs) are commonly used in transition‐metal‐catalyzed cycloadditions, and the utilization of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium‐catalyzed, visible‐light‐driven, asymmetric [5+2] cycloaddition of VCPs with α‐diazoketones is accomplished by switching the reactivity of the Pd‐containing dipolar intermediate from an all‐carbon 1,3‐dipole to an oxo‐1,5‐dipole. Enantioenriched seven‐membered lactones were produced with good reaction efficiencies and selectivities (23 examples, 52–92 % yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo‐ and periselectivities.