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Published January 7, 2020 | Accepted Version + Supplemental Material
Journal Article Open

Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation-Binding Salen Nickel Complexes

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 (K_a=6.6×10⁵ M⁻¹).

Additional Information

© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Accepted manuscript online: 12 November 2019; Manuscript accepted: 11 November 2019; Manuscript revised: 06 November 2019; Manuscript received: 12 October 2019. This work was supported by the "GIST‐Caltech Research Collaboration" grant funded by the GIST in 2017, and by the National Research Foundation of Korea grant funded by the Korean Government (NRF‐2012R1A1A2044550, NRF‐2017M1A2A2049102). The NIH‐NIGMS (R01GM080269) and Caltech are also thanked for support of our research program. C.I.J. thanks the National Science Foundation for a predoctoral fellowship. The authors declare no conflict of interest.

Attached Files

Accepted Version - Park_et_al-2019-Angewandte_Chemie_International_Edition.pdf

Supplemental Material - anie201913057-s1-supporting_information_nialkynylation-compiled-r7.pdf

Files

Park_et_al-2019-Angewandte_Chemie_International_Edition.pdf

Additional details

Created:
August 22, 2023
Modified:
October 18, 2023