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Synthesis 2021; 53(21): 3935-3950
DOI: 10.1055/a-1547-9270
DOI: 10.1055/a-1547-9270
short review
Fluorine-Retentive Strategies for the Functionalization of gem-Difluoroalkenes
Generous financial support from the National Institute of General Medical Sciences of the National Institutes of Health (R35 GM124661) is gratefully acknowledged. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health.
Abstract
gem-Difluoroalkenes are readily available fluorinated building blocks, and the fluorine-induced electronic perturbations of the alkenes enable a wide array of selective functionalization reactions. However, many reactions of gem-difluoroalkenes result in a net C–F functionalization to generate monofluorovinyl products or addition of F to generate trifluoromethyl-containing products. In contrast, fluorine-retentive strategies for the functionalization of gem-difluoroalkenes remain less generally developed and is now becoming a rapidly developing area. This review will present the development of fluorine-retentive strategies including electrophilic, nucleophilic, radical, and transition metal catalytic strategies with an emphasis on key physical organic and mechanistic aspects that enable reactivities.
1 Introduction
2 Two-Electron Processes
2.1 Elimination of Allyl Groups
2.2 Electrophilic Addition
2.3 Halonium and Thiiranium Intermediates
2.4 Kinetic Quench of Anionic Intermediates
2.5 Concerted Cycloadditions
3 Radical Processes
3.1 Thermal Activation
3.2 Photoactivation
3.3 Transition-Metal-Mediated
4 Reductions
5 Cross-Coupling Reactions
6 Conclusions
Publication History
Received: 13 May 2021
Accepted after revision: 12 July 2021
Accepted Manuscript online:
12 July 2021
Article published online:
25 August 2021
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