A Highly Enantioselective Catalyst for the Asymmetric Nozaki–Hiyama–Kishi Reaction of Allylic and Vinylic Halides


  • This work was supported by the European Community (Research Training Network “Combinatorial Catalysis”) and by the Fonds der Chemischen Industrie. We thank Dr. Ira Fiolia for technical support.


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Catalytic asymmetric addition of vinylic halides and triflates to aldehydes, with useful levels of stereoinduction, has been achieved for the first time using the salen-type ligand (S,S)-5 (see scheme; PMB=para-methoxybenzyl), which contains the novel endo,endo-2,5-diamino norbornane building block. This asymmetric Nozaki–Hiyama–Kishi reaction leads to the coupling of various halides and aldehydes with high yields and enantioselectivities (up to 92 % ee).