56135-01-4

Upstream product

• 56134-98-6 Methyl-3,3-difluor-2,3-dichlor-2-phenyl-propionat 
• 22979-35-7 Methyl phenyldiazoacetate 
• 115262-01-6 [bromo(difluoro)methyl]-trimethyl-silane 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 101-41-7 benzeneacetic acid methyl ester 
• 36853-08-4 2-(chloro-difluoro-methyl)-3,3-difluoro-2-phenyl-oxirane 

Downstream Products

• 37434-59-6 dimethyl 2-phenylmalonate 
• 184414-29-7 methyl 3,3,3-trifluoro-2-phenylpropanoate 

Relevant academic research and scientific papers

Cross-Coupling between Difluorocarbene and Carbene-Derived Intermediates Generated from Diazocompounds for the Synthesis of gem-Difluoroolefins

Cross-coupling between difluorocarbene and carbene-derived intermediates generated from diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gem-difluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper-difluorocarbene complex was proposed.

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.