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Csp^3-Csp^3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes

Paeth, Matthew and Tyndall, Sam B. and Chen, Liang-Yu and Hong, Jia-Cheng and Carson, William P. and Liu, Xingwu and Sun, Xiaodong and Liu, Jinjia and Yang, Kundi and Hale, Elizabeth M. and Tierney, David L. and Liu, Bin and Cao, Zhi and Cheng, Mu-Jeng and Goddard, William A., III and Liu, Wei (2019) Csp^3-Csp^3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. Journal of the American Chemical Society, 141 (7). pp. 3153-3159. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20190125-155529881

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Abstract

Carbon–carbon bond-forming reductive elimination from elusive organocopper(III) complexes has been considered the key step in many copper-catalyzed and organocuprate reactions. However, organocopper(III) complexes with well-defined structures that can undergo reductive elimination are extremely rare, especially for the formation of Csp^3–Csp^3 bonds. We report herein a general method for the synthesis of a series of [alkyl-Cu^(III)-(CF_3)_3]^− complexes, the structures of which have been unequivocally characterized by NMR spectroscopy, mass spectrometry, and X-ray crystal diffraction. At elevated temperature, these complexes undergo reductive elimination following first-order kinetics, forming alkyl-CF3 products with good yields (up to 91%). Both kinetic studies and DFT calculations indicate that the reductive elimination to form Csp^3–CF^3 bonds proceeds through a concerted transition state, with a ΔH⧧ = 20 kcal/mol barrier.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b12632DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b12632PublisherSupporting Information
ORCID:
AuthorORCID
Liu, Xingwu0000-0002-8564-1151
Cheng, Mu-Jeng0000-0002-8121-0485
Goddard, William A., III0000-0003-0097-5716
Liu, Wei0000-0001-6249-3179
Alternate Title:Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes
Additional Information:© 2019 American Chemical Society. Received: November 25, 2018; Published: January 25, 2019. W.L. thanks Miami University for the start-up funding. L.-Y.C., J.-C.H., and M.-J.C. acknowledge financial support from the Ministry of Science and Technology of the Republic of China under grant no. MOST 107-2113-M-006-008-MY2. We also thank Dr. Theresa Ramelot for assistance with HR-ESI and Prof. John Rakovan for assistance with X-ray crystal diffraction. W.A.G. acknowledges financial support from NSF (NSF CBET 1512759). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Miami UniversityUNSPECIFIED
Ministry of Science and Technology (China)MOST 107-2113-M-006-008-MY2
NSFCBET-1512759
Subject Keywords:Trifluoromethyl; reductive elimination; high-valent copper; DFT calculation; organometallic reactions
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1321
Record Number:CaltechAUTHORS:20190125-155529881
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190125-155529881
Official Citation:Csp3–Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. Matthew Paeth, Sam B. Tyndall, Liang-Yu Chen, Jia-Cheng Hong, William P. Carson, Xingwu Liu, Xiaodong Sun, Jinjia Liu, Kundi Yang, Elizabeth M. Hale, David L. Tierney, Bin Liu, Zhi Cao, Mu-Jeng Cheng, William A. Goddard III, and Wei Liu. Journal of the American Chemical Society 2019 141 (7), 3153-3159. DOI: 10.1021/jacs.8b12632
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92483
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Jan 2019 17:59
Last Modified:22 Mar 2019 17:04

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