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
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Additional details
- Eprint ID
- 99801
- DOI
- 10.1002/anie.201913057
- Resolver ID
- CaltechAUTHORS:20191112-095230680
- Gwangju Institute of Science and Technology (GIST)
- National Research Foundation of Korea
- 2012R1A1A2044550
- National Research Foundation of Korea
- 2017M1A2A2049102
- NIH
- R01GM080269
- Caltech
- NSF Predoctoral Fellowship
- Created
-
2019-11-12Created from EPrint's datestamp field
- Updated
-
2021-11-16Created from EPrint's last_modified field