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Enantioselective Palladium-Catalyzed Directed Migratory Allylation of Remote Dienes |
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| Authors: | Dr. Xian-Xiao Chen Hao Luo Ye-Wei Chen Yang Liu Prof. Zhi-Tao He |
| Affiliation: | 1. 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.;2. CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032 China |
| Abstract: | Chain walking has been an efficient route to realize the functionalization of inert C(sp3)−H bonds, but this strategy is limited to mono-olefin migration and functionalization. Herein, we demonstrate the feasibility of tandem directed simultaneous migrations of remote olefins and stereoselective allylation for the first time. The adoption of palladium hydride catalysis and secondary amine morpholine as solvent is critical for achieving high substrate compatibility and stereochemical control with this method. The protocol is also applicable to the functionalization of three vicinal C(sp3)−H bonds and thus construct three continuous stereocenters along a propylidene moiety via a short synthetic process. Preliminary mechanistic experiments corroborated the design of simultaneous walking of remote dienes. |
| Keywords: | Asymmetric Catalysis Chain Walking Migratory Allylation Palladium Remote Dienes |