Claisen rearrangement over the past nine decades.

1,1-Dihalo-1-alkenes are valuable synthetic tools in organic
chemistry and serve as interesting synthetic intermediates in a variety of non-metal-assisted chemical transformations. Moreover, the vinyl dihalide functionality is an attractive and versatile bidentate electrophile for organometallic chemistry.

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

gem-Difluoroolefin synthesis: general methods via thermostable difluorovinylmetals starting from 2,2,2-trifluoroethanol derivatives

Thanks to the beneficial effect of fluorine substitution on the pharmacokinetic properties of molecules, an ever increasing number of marketed drugs incorporate a fluorine atom into their structure. As a consequence, the synthesis of fluorinated molecules has become a very active research field. Among the numerous approaches, fluorinated enol ethers are valuable building blocks that allow the introduction of a fluoro- or difluoromethyl group through a wide variety of reactions. The present review lists different methods for their preparation and sums up their numerous synthetic applications.

Fluorinated enol ethers: their synthesis and reactivity

Photoredox-catalyzed hydrodifluoroalkylation of alkenes proceeded smoothly in the presence of a Hantzsch ester as a hydrogen source under visible light irradiation. The reaction was also applicable to the hydrodifluoroalkylation of alkynes, and a continuous photo flow reaction was also successful.

Photoredox-Catalyzed Hydrodifluoroalkylation of Alkenes Using Difluorohaloalkyl Compounds and a Hantzsch Ester

A new route to 1,1-difluoroolefins

Claisen rearrangement of allylfluorovinyl ethers

Claisen Rearrangement of Allyl Bromofluorovinyl Ethers

Reactivity of 1-bromo-1,1-difluoro-2-alkenes: Synthesis of 1,1-difluoroolefins

A new method for the synthesis of various 1,1-difluoroolefins is described. The key step is the treatment of 1-bromo-1,1-difluoro-2-alkenes with organo-metallic reagents in the presence of copper and lithium salts.

Monique Baudry

Papers

A new route to 1,1-difluoroolefins

Claisen rearrangement of allylfluorovinyl ethers

Claisen Rearrangement of Allyl Bromofluorovinyl Ethers

Reactivity of 1-bromo-1,1-difluoro-2-alkenes: Synthesis of 1,1-difluoroolefins

A New Route to 1,1-Difluoroolefins.