700-59-4Relevant academic research and scientific papers
Reinvestigation of the Wadsworth-Emmons reaction involving lithium difluoromethylenephosphonate
Piettre, Serge R.,Cabanas, Leonora
, p. 5881 - 5884 (1996)
Application of the published reaction conditions for the Wadsworth-Emmons transformation of ketones or aldehydes into 1,1-difluoroolefins with lithium difluoromethylenephosphonate failed to give the expected product, affording instead phosphates of the ge
Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms
Andrella, Nicholas O.,Xu, Nancy,Gabidullin, Bulat M.,Ehm, Christian,Baker, R. Tom
supporting information, p. 11506 - 11521 (2019/08/20)
The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene dimer affords a single isomer of heptafluoro-2-methylpentene in which five fluorines have been selectively replaced with hydrogens. DFT computational studies suggest a distinct HDF mechanisms for L2CuH (bidentate or bulky monodentate phosphines) and L3CuH (small cone angle monodentate phosphines) catalysts, allowing for stereocontrol of the HDF of trifluoroethylene.
Photocatalytic alkene reduction by a B12-TiO2 hybrid catalyst coupled with C-F bond cleavage for: Gem -difluoroolefin synthesis
Tian, Hui,Shimakoshi, Hisashi,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio
supporting information, p. 9478 - 9481 (2017/09/01)
Photocatalytic syntheses of gem-difluoroolefins were performed using the B12-TiO2 hybrid catalyst during the CC bond reduction of α-trifluoromethyl styrenes with C-F bond cleavage at room temperature under nitrogen. The gem-difluoroolefins were used as synthetic precursors for fluorinated cyclopropanes.
Synthesis of 1,1-difluoroalkenes via α,α-difluoro-β-lactones
Ocampo, Rogelio,Dolbier, William R.,Paredes, Rodrigo
, p. 41 - 50 (2007/10/03)
A new method for the general synthesis of 1,1-difluoroalkenes from ketones is presented.The procedure involves initial condensation of a ketone with the difluoro Reformatsky reagent, hydrolysis to form the α,α-difluoro-β-hydroxy acids, followed by cycliza
DIFLUOROMETHYLDIPHENYLPHOSPHINE OXIDE. A NEW REAGENT FOR CONVERSION OF CARBONYL COMPOUNDS TO 1,1-DIFLUOROOLEFINS
Edwards, Michael L.,Stemerick, David M.,Jarvi, Esa T.
, p. 5571 - 5574 (2007/10/02)
Difluoromethyldiphenylphosphine oxide (5) was synthesized from chlorodifluoromethane and diphenylphosphine oxide.Reaction of 5 with a variety of ketones and aldehydes gave 1,1-difluoroolefins.Monofluoromethyldiphenylphosphine oxide (7) was also synthesize
Ylide-Carbene Chemistry. Synthesis of 1,1-Difluoro-1-alkenes
Wheaton, Gregory A.,Burton, Donald J.
, p. 917 - 927 (2007/10/02)
The reaction between nonstabilized alkylidenetriphenylphosphoranes and chlorodifluoromethane has been found to be a useful alternative to the Wittig reaction for the synthesis of many difluoromethylene olefins.Both primary and secondary ylides which do not contain strongly electron-withdrawing substituents within the alkylidene portion of the ylide react with chlorodifluoromethane to give the corresponding difluoromethylene olefins in yields which are significantly better than those obtained by the Wittig reaction.The formation of triphenylphosphine oxide is avoided, and all phosphorus-containing moieties can be recovered and recycled.The reaction proceeds by initial dehydrochlorination of chlorodifluoromethane by the ylide to generate difluorocarbene.The intermediate difluorocarbene is then trapped by a second equivalent of the nucleophilic ylide.Mechanistic evidence indicates that either a zwitterionic intermediate or a three-membered cyclic phosphorane can account for the 1,1-difluoro-1-alkene products.The isolation of several 1-hydro-1-fluoro-1-alkene products such as FCH=CHPh, FHC=CPh2, and FHC=CHCH=CHPh after steam distillation of the reaction mixtures, however, can only be accounted for via a three-membered cyclic phosphorane.
PREPARATION AND SYNTHETIC UTILITY OF FLUORINATED PHOSPHONIUM SALTS, BISPHOSPHONIUM SALTS AND PHOSPHORANIUM SALTS
Burton, Donald J.
, p. 339 - 358 (2007/10/02)
The reaction of tertiary phosphines with fluorohalomethanes provides a rapid and high yield synthesis of various types of fluorinated phosphonium salts, bis-phosphonium salts and phosphoranium salts.These salts are useful precursors to fluorine-containing
