Asymmetric (4+1) Annulations by Cascade Allylation and Transient σ-Alkyl-Pd(II) Initiated Allylic Csp3−H Activation
Haiyu Sun
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, Yanxiang Road 99, Xi'an, 710045 China
Search for more papers by this authorHui He
Department of Chemistry, Shantou University, Shantou, 515063 China
Search for more papers by this authorDr. Shao-Fei Ni
Department of Chemistry, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Wusheng Guo
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, Yanxiang Road 99, Xi'an, 710045 China
Search for more papers by this authorHaiyu Sun
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, Yanxiang Road 99, Xi'an, 710045 China
Search for more papers by this authorHui He
Department of Chemistry, Shantou University, Shantou, 515063 China
Search for more papers by this authorDr. Shao-Fei Ni
Department of Chemistry, Shantou University, Shantou, 515063 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Wusheng Guo
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, Yanxiang Road 99, Xi'an, 710045 China
Search for more papers by this authorAbstract
A unique Pd-catalyzed approach for asymmetric (4+1) annulations via cascade allylation and transient σ-alkyl-Pd(II) initiated methylene Csp3−H activation is reported. The enolate fragment derived from the decarboxylation of vinyl methylene carbonate is crucial to stabilize the key intermediate. These reactions enable the synthesis of various useful dihydrobenzofurans with excellent enantioselectivity, typically >95 : 5 er, and exclusive (Z)-stereoselectivity. Compared with the well-established annulations via Heck-type C−H activations, this protocol showcases a conceptually new way to generate σ-alkyl-Pd(II) species that could initiate challenging asymmetric Csp3−H activations.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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