The Cyano Group as a Traceless Activation Group for the Intermolecular [3+2] Cycloaddition of Azomethine Ylides: A Five-Step Synthesis of (±)-Isoretronecanol†
Jundong Li
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorHuaibo Zhao
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorXunjin Jiang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorXiance Wang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorHaiming Hu
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorLei Yu
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Yandong Zhang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)Search for more papers by this authorJundong Li
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorHuaibo Zhao
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorXunjin Jiang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorXiance Wang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorHaiming Hu
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorLei Yu
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Yandong Zhang
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (P.R. China)Search for more papers by this authorThis research was supported by the Opening Foundation of the Laboratory of Chemical Genomics of Peking University Shenzhen Graduate School, the NSFC (21142007 and 21272194), the RFDP (20110121120014), the NSFFJ (2012J01055), the NFFTBS (J1310024), the FRFCU (2012121017), the SRF for ROCS of SEM, and the Program for Changjiang Scholars and Innovative Research Teams in University (PCSIRT). We also thank Prof. Tingbin Wen and Jie Ouyang for the help with X-ray crystallographic analysis and 11B NMR spectroscopic experiments.
Graphical Abstract
Without a trace…︁ A highly stereoselective cycloaddition strategy provided efficient access to a diverse array of 5-unsubstituted pyrrolidines and enabled a five-step total synthesis of isoretronecanol (see scheme). A novel role of sodium borohydride in reductive decyanation was observed.
Abstract
The cyano group was used as a traceless activation group for the [3+2] cycloaddition of azomethine ylides in a two-step process, thereby providing a highly effective approach to 5-unsubstituted pyrrolidines. The transformation includes the silver acetate catalyzed intermolecular 1,3-dipolar cycloaddition of α-iminonitriles and an unprecedented sodium borohydride induced reductive decyanation reaction. A diverse array of substrates is amenable to this transformation. The methodology was further extended to a five-step total synthesis of the pyrrolizidine natural product isoretronecanol.
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