Synthesis of Fluoroolefins via Julia-Kocienski Olefination

Abstract

The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

1 Introduction

2 Synthesis of Fluorostilbene-like and Fluorostyrene-like Derivatives

3 Synthesis of Fluoroalkylidenes

3.1 Benzothiazole-Based Reagents

3.2 Phenyltetrazole-Based Reagents

4 Synthesis of Functionalized Fluoroolefins

4.1 α-Fluoroacrylates

4.1.1 Benzothiazole- and Phenyltetrazole-Based Reagents

4.1.2 Bis(trifluoromethyl)phenyl-Based Reagents

4.2 α-Fluoroacrylonitriles

4.3 α-Fluorovinyl Phenyl Sulfones

4.4 α-Fluorovinyl Weinreb Amides

4.4.1 Bis(trifluoromethyl)phenyl-Based Reagent

4.4.2 Benzothiazole-Based Reagent

4.5 α-Fluoroenones

5 Synthesis of 1,1-Difluoroalkenes

6 Mechanism of Julia-Kocienski Olefination

7 Miscellaneous Syntheses of Heteroaryl-Derived Fluorinated Sulfides and Sulfones

8 Conclusions

Key words

Julia-Kocienski olefination - fluoroalkenes - fluoro sulfones - alkenation reagents - electrophilic fluorination

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49

For the purpose of comparison, 2-naphthaldehyde was reacted with 15 in the presence of MgBr₂, using the same conditions as those reported for 47 (ref. 35). Fluoroalkene was obtained in 14:86 E/Z ratio, consistent with reported results (ref. 32a).