Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine
نویسندگان
چکیده
BACKGROUND 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods. RESULTS The combination of (chlorodifluoromethyl)trimethylsilane (TMSCF2Cl) and triphenylphosphine (PPh3) can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyl)trimethylsilane (TMSCF2Br) and (trifluoromethyl)trimethylsilane (TMSCF3) in this reaction. CONCLUSION Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.
منابع مشابه
Difluoromethyl 2-pyridyl sulfone: a versatile carbonyl gem-difluoroolefination reagent
Fluoroalkenes have attracted extensive research interest from the synthetic community for decades owing to their unique properties and important applications. Recently, exploring new reagents and methods for the synthesis of gem-difluoroolefins with high reliability and broad scope has become particularly active. Taking into account the cost and availability of the starting materials, the deoxy...
متن کاملgem-Difluoroolefination of diaryl ketones and enolizable aldehydes with difluoromethyl 2-pyridyl sulfone: new insights into the Julia-Kocienski reaction.
The direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rear...
متن کاملAn easy access to fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazones.
An efficient and operationally simple synthesis of fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazone surrogates is reported. The reaction can be carried out in a one-pot procedure directly from carbonyl compounds.
متن کاملThe Reaction of (h5-Cyclopentadienyl)carbonyl(triphenylphosphine)iridium and Bis(pentafluorophenyl)acetylene
M. D. Rausch* and R. G. Gastinger Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, USA Z. Naturforsch. 34b, 700-705 (1979); received January 9, 1979 Metallocycles, Organo-Iridium Compounds, Oxidative Addition The reaction between (h5-cyclopentadienyl)carbonyl(triphenylphosphine)iridium and bis(pentafluorophenyl)acetylene has been investigated in detail. As in ...
متن کاملA facile catalyst-free synthesis of gem-dihydroperoxides with aqueous hydrogen peroxide.
gem-Dihydroperoxides were easily obtained from the corresponding carbonyl compounds in high yields through a catalyst-free method with aqueous H(2)O(2) (35%) in 1,2-dimethoxyethane at room temperature.
متن کامل