A Nickel-Catalyzed Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for Alkylcyclopropane Synthesis: Investigation of Stereochemical Outcomes and Radical Lifetimes.
| Autor: | Chen PP; Center of Chemistry for Frontiers Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China., McGinnis TM; Department of Chemistry, University of California, Irvine, California 92697, United States., Lin PC; Department of Chemistry, University of California, Irvine, California 92697, United States., Hong X; Center of Chemistry for Frontiers Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China.; Beijing National Laboratory for Molecular Sciences, Zhongguancun North First Street No. 2, Beijing 100190, China.; Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, China., Jarvo ER; Department of Chemistry, University of California, Irvine, California 92697, United States. |
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| Jazyk: | angličtina |
| Zdroj: | ACS catalysis [ACS Catal] 2023 Apr 07; Vol. 13 (8), pp. 5472-5481. Date of Electronic Publication: 2023 Apr 07 (Print Publication: 2023). |
| DOI: | 10.1021/acscatal.3c00905 |
| Abstrakt: | Understanding mechanistic details of the nickel-catalyzed coupling reactions of Csp 3 alcohol derivatives is key to developing selective reactions of this widely prevalent functional group. In this manuscript, we utilize a combination of experimental data and DFT studies to define the key intermediates, stereochemical outcome, and competing pathways of a nickel-catalyzed cross-electrophile coupling reaction of 1,3-dimesylates. Stereospecific formation of a 1,3-diiodide intermediate is achieved in situ by the Grignard reagent. The overall stereoablative stereochemical outcome is due to a nickel-catalyzed halogen atom abstraction with a radical rebound that is slower than epimerization of the alkyl radical. Finally, lifetimes of this alkyl radical intermediate are compared to radical clocks to enhance the understanding of the lifetime of the secondary alkyl radical. Competing Interests: The authors declare no competing financial interest. (© 2023 The Authors. Published by American Chemical Society.) |
| Databáze: | MEDLINE |
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