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Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation‐Binding Salen Nickel Complexes
Authors:Dongseong Park  Carina I Jette  Jiyun Kim  Woo‐Ok Jung  Yongmin Lee  Jongwoo Park  Seungyoon Kang  Min Su Han  Brian M Stoltz  Sukwon Hong
Abstract:Cation‐binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10–20 mol % KOt‐Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo‐selectivity was observed, generating 1,2‐addition products exclusively over 1,4‐addition products. UV‐vis analysis revealed the pendant oligo‐ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (Ka=6.6×105 m ?1).
Keywords:alkynylation  bifunctional catalysis  nickel  trifluoromethylketones
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