Synthesis of gem-Difluoromethylenated Compounds Employing α,α-Difluoro-α-phenylsulfanyl-α-trimethylsilylmethane (PhSCF₂SiMe₃) as a gem-Difluoromethylene Building Block

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

Key words

fluorine - radical cyclization - sulfur - indolizidines - pyrrolizidines - succinic anhydrides - succinimides

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