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Synlett 2014; 25(18): 2558-2573
DOI: 10.1055/s-0034-1379164
DOI: 10.1055/s-0034-1379164
account
Synthesis of gem-Difluoromethylenated Compounds Employing α,α-Difluoro-α-phenylsulfanyl-α-trimethylsilylmethane (PhSCF2SiMe3) as a gem-Difluoromethylene Building Block
Further Information
Publication History
Received: 28 July 2014
Accepted after revision: 26 August 2014
Publication Date:
15 October 2014 (online)
Abstract
α,α-Difluoro-α-phenylsulfanyl-α-trimethylsilylmethane (PhSCF2SiMe3) is a synthetically important fluorinating reagent. This account summarizes our work on the synthetic utility of α,α-difluoro-α-phenylsulfanyl-α-trimethylsilylmethane as a versatile gem-difluoromethylene building block for the preparation of a variety of gem-difluoromethylenated compounds.
1 Introduction
2 Fluoride-Catalyzed Nucleophilic Addition of PhSCF2SiMe3 to Carbonyl Compounds
2.1 Synthesis of gem-Difluoromethyl Aryl Ketones
2.2 Synthesis of gem-1,1-Difluoroalkenes
2.3 Synthesis of gem-Difluoromethylenated Cyclopentanol Derivatives
3 Fluoride-Catalyzed Nucleophilic Addition of PhSCF2SiMe3 to N-Substituted Phthalimides and Succinimide Derivatives
3.1 Synthesis of gem-Difluoromethylenated 1-Azabicyclic Compounds
3.2 Asymmetric Synthesis of gem-Difluoromethylenated Pyrrolizidines and Indolizidines
4 Fluoride-Catalyzed Nucleophilic Addition of PhSCF2SiMe3 to Anhydride Derivatives
5 Fluoride-Catalyzed Chemoselective Nucleophilic Addition of PhSCF2SiMe3 to Keto Esters
5.1 Synthesis of gem-Difluoromethylenated Spiro-γ-butyrolactones
5.2 Synthesis of gem-Difluoromethylenated Bicyclo[m.n.0]-alkan-1-ols and Their Ring-Expansion into gem-Difluoromethylenated Macrocyclic Lactones
6 Asymmetric Synthesis of 3,3-Difluoro-2-propanoylbicyclo[3.3.0]octanes
7 Conclusions
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References and Notes
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For selected examples of difluoromethylation, see:
For the activation of trimethylsilyl (TMS) derivatives with Lewis bases, see for example: