Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation‐Binding Salen Nickel Complexes. Issue 2 (2nd December 2019)

• Record Type: Journal Article
• Authors: Park, Dongseong; Jette, Carina I.; Kim, Jiyun; Jung, Woo‐Ok; Lee, Yongmin; Park, Jongwoo; Kang, Seungyoon; Han, Min Su; Stoltz, Brian M.; Hong, Sukwon
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 2(2020)
• Page Start: 775
• Page End: 779
• Publication Date: 2019-12-02
• Subjects: alkynylation -- bifunctional catalysis -- nickel -- trifluoromethylketones; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201913057
• Languages: English
• ISSNs: 1433-7851

Abstract

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 % KO t ‐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 ( K a =6.6×10 5 m −1 ). 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 % KO t ‐Bu) and open to air. UV/vis analysis revealed the pendant oligo‐ether group of the catalyst strongly binds to the potassium cation with 1:1 binding stoichiometry ( K a =6.6×10 5 m −1 ).