A photocatalytic process was devised to synthesize monofluoroalkenes via defluorinative functionalization of allylic difluorides. -Alkylanilines are used as precursors to α-aminoalkyl radicals, which undergo regioselective addition to allylic difluorides, and subsequent SET and fluoride elimination produce monofluoroalkenes. C-C bond formation on the aniline is site-selective for the least substituted carbon α to nitrogen.
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http://dx.doi.org/10.1021/acs.joc.4c01861 | DOI Listing |
Org Lett
November 2024
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
Significant progress has been made in the synthesis of diverse ketals through a palladium-catalyzed reaction involving allylic -difluorides and various phenols or alcohols. This methodology facilitates double -defluoroetherification of allylic -difluorides, resulting in high product yields with excellent regioselectivity. The reactions were conducted under mild conditions and exhibited outstanding tolerance to a wide range of functional groups.
View Article and Find Full Text PDFJ Org Chem
September 2024
Canadian Centre for Research in Advanced Fluorine Technologies, Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive, Lethbridge, Alberta T1K 3M4, Canada.
A photocatalytic process was devised to synthesize monofluoroalkenes via defluorinative functionalization of allylic difluorides. -Alkylanilines are used as precursors to α-aminoalkyl radicals, which undergo regioselective addition to allylic difluorides, and subsequent SET and fluoride elimination produce monofluoroalkenes. C-C bond formation on the aniline is site-selective for the least substituted carbon α to nitrogen.
View Article and Find Full Text PDFNat Commun
May 2024
West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610041, China.
Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by the inherent preference for an inner-sphere mechanism. Here, we present a demonstration of an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates. This unconventional mechanism offers an opportunity for the fluorine recycling of gem-difluorinated cyclopropanes via C - F bond cleavage/reformation, ultimately delivering allylic carbofluorination products.
View Article and Find Full Text PDFChem Commun (Camb)
April 2024
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Chang-zhou University, Changzhou, 213164, China.
Herein, a palladium-catalyzed regioselective alkynylation, esterification, and amination of allylic -difluorides C-F bond activation/transmetallation/β-C elimination or nucleophilic attack has been achieved. This innovative protocol showcases an extensive substrate range and operates efficiently under mild reaction conditions, resulting in high product yields and -selectivity. Particularly noteworthy is its exceptional tolerance towards a wide array of functional groups.
View Article and Find Full Text PDFOrg Lett
December 2023
Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
Significant advancements in synthesis of monofluoroalkenes via palladium-catalyzed reactions involving allylic -difluorides and diverse nucleophiles have been achieved. This method allows regioselective arylation, alkylation, allylation, alkenylation, and hydrogenation of allylic -difluorides, yielding high selectivity and favorable product yields under mild conditions. Tolerating various functional groups, these transformations utilize a common Pd-OH intermediate.
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