Umpolung Asymmetric 1,5-Conjugate Addition via Palladium Hydride Catalysis
Yu-Chao Wang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou, 341000 China
These authors contributed equally to this work.
Search for more papers by this authorZhao-Xin Xiao
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
These authors contributed equally to this work.
Search for more papers by this authorMiao Wang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
These authors contributed equally to this work.
Search for more papers by this authorShao-Qian Yang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
Search for more papers by this authorProf. Jin-Biao Liu
Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou, 341000 China
Search for more papers by this authorCorresponding Author
Prof. Zhi-Tao He
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024 China
Search for more papers by this authorYu-Chao Wang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou, 341000 China
These authors contributed equally to this work.
Search for more papers by this authorZhao-Xin Xiao
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
These authors contributed equally to this work.
Search for more papers by this authorMiao Wang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
These authors contributed equally to this work.
Search for more papers by this authorShao-Qian Yang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
Search for more papers by this authorProf. Jin-Biao Liu
Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou, 341000 China
Search for more papers by this authorCorresponding Author
Prof. Zhi-Tao He
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024 China
Search for more papers by this authorAbstract
Electronically matched nucleophilic 1,6-conjugate addition has been well studied and widely applied in synthetic areas. In contrast, nucleophilic 1,5-conjugate addition represents an electronically forbidden process and is considered unfeasible. Here, we describe modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis. Both palladium and synergistic Pd/organocatalyst systems are developed to catalyze 1,5-conjugate reaction, followed by inter- or intramolecular [3+2] cyclization. A migratory 1,5-addition protocol is established to corroborate the feasibility of this umpolung concept. The 1,5-addition products are conveniently transformed into a series of privileged enantioenriched motifs, including polysubstituted tetrahydrofuran, dihydrofuran, cyclopropane, cyclobutane, azetidine, oxetane, thietane, spirocycle and bridged rings. Preliminary mechanistic studies corroborate the involvement of palladium hydride catalysis.
Conflict of interest
The authors declare no conflict of interest.
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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