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. doi:10.1002/anie.201913057. 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:

URL	URL Type	Description
https://doi.org/10.1002/anie.201913057	DOI	Article

ORCID:

Author	ORCID
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 Agency	Grant Number
Gwangju Institute of Science and Technology (GIST)	UNSPECIFIED
National Research Foundation of Korea	2012R1A1A2044550
National Research Foundation of Korea	2017M1A2A2049102
NIH	R01GM080269
Caltech	UNSPECIFIED
NSF Predoctoral Fellowship	UNSPECIFIED

Subject Keywords:

nickel; Bifunctional Catalysis; Alkynylation; Trifluoromethylketones

Issue or Number:

DOI:

10.1002/anie.201913057

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

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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:

16 Nov 2021 17:49

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