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

Park, Dongseong and Jette, Carina I. and Kim, Jiyun and Jung, Woo-ok and Lee, Yongmin and Park, Jongwoo and Kang, Seungyoon and Han, Min Su and Stoltz, Brian M. and Hong, Sukwon (2020) Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation-Binding Salen Nickel Complexes. Angewandte Chemie International Edition, 59 (2). pp. 775-779. ISSN 1433-7851. https://resolver.caltech.edu/CaltechAUTHORS:20191112-095230680

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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).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.201913057DOIArticle
ORCID:
AuthorORCID
Jette, Carina I.0000-0002-8476-6032
Stoltz, Brian M.0000-0001-9837-1528
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.
Funders:
Funding AgencyGrant Number
Gwangju Institute of Science and Technology (GIST)UNSPECIFIED
National Research Foundation of Korea2012R1A1A2044550
National Research Foundation of Korea2017M1A2A2049102
NIHR01GM080269
CaltechUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Subject Keywords:nickel; Bifunctional Catalysis; Alkynylation; Trifluoromethylketones
Issue or Number:2
Record Number:CaltechAUTHORS:20191112-095230680
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20191112-095230680
Official Citation:D. Park, C. I. Jette, J. Kim, W.-O. Jung, Y. Lee, J. Park, S. Kang, M. S. Han, B. M. Stoltz, S. Hong, Angew. Chem. Int. Ed. 2020, 59, 775. doi: 10.1002/anie.201913057
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:99801
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Nov 2019 21:17
Last Modified:08 Jan 2020 19:44

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