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Synlett 2016; 27(20): 2747-2755
DOI: 10.1055/s-0036-1588637
DOI: 10.1055/s-0036-1588637
synpacts
Metal-Catalyzed Decarboxylative Fluoroalkylation Reactions
Further Information
Publication History
Received: 22 August 2016
Accepted after revision: 06 October 2016
Publication Date:
25 October 2016 (online)
Abstract
Metal-catalyzed decarboxylative fluoroalkylation reactions enable the conversion of simple O-based substrates into biologically relevant fluorinated analogues. Herein, we present decarboxylative methods that facilitate the synthesis of trifluoromethyl- and difluoroketone-containing products. We highlight key mechanistic aspects that are critical for efficient catalysis, and that inspired our thinking while developing the reactions.
1 Introduction
2 Copper-Catalyzed Decarboxylative Trifluoromethylation Reactions
2.1 Net Trifluoromethylation of Alcohols
2.2 Mechanism of Decarboxylation Impacts Functional-Group Tolerance
2.3 Allylic Trifluoromethylation Enabled by Activation Protocol
2.4 Generation of Iodide Intermediate Required for Benzylic Trifluoromethylation
2.5 Ligand-Controlled Regiodivergent Trifluoromethylation of Propargylic Electrophiles
2.6 Summary
3 Palladium-Catalyzed Decarboxylative Alkylation of α,α-Difluoroketone Enolates
3.1 Convergent Routes towards α,α-Difluoroketones
3.2 Palladium-Catalyzed Decarboxylative Benzylation of α,α-Difluoroketone Enolates
3.3 Palladium-Catalyzed Decarboxylative Allylation of α,α-Difluoroketone Enolates
3.4 Summary
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