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藉由兩種不飽和組件的還原偶合反應來建構碳-碳鍵的生成
Dissertation

藉由兩種不飽和組件的還原偶合反應來建構碳-碳鍵的生成

葉建宏
Doctor of Philosophy (PHD), 國立清華大學, 化學系
2011

Abstract

還原偶合 Nickel Zinc Ammonia Reductive Coupling
The C-C bond construction via reductive coupling reaction (RCR) is a convenient tool for organic synthesis. In our lab, we have achieved various RCRs between different π-components which were based on catalytic amount of nickel/cobalt complex combined with stoichiometric amount of zinc as a system from several years ago. In this thesis, we go further to explore different RCRs based on previous study and develop RCR with novel fashion to wide-broad application. Here, we discuss three types of RCR: (1) Nickel catalyzed intermolecular RCR of imines and activated alkenes. (2) Zinc-ammonia mediated various RCRs: “aryl carbonyls and activated alkenes”, “electron withdrawing ketones and activated alkenes”, “phthalimide and activated alkenes”. (3) Ammonia promoted zinc insertion of sp2-carbon halide bond: direct conjugate addition of functional aryl bromides with activated alkenes. Especially, zinc ammonia mediated RCR which equips high regioselectivity, low cost, high tolerance of functional group, reaction proceeds under room temperature and atmospheric pressure. It’s a reliable way to synthesize a series of γ-hydroxybutyric acid precursors, γ-lactone derivatives, 4-hydroxy-(E)-2-alkenoic esters and 3-hydroxyisoindolin -1-one derivatives. However, the mechanism of zinc-ammonia mediated RCR is unclear for us to date. We wish to have further study and get the insight into interaction of zinc and ammonia in the future.

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