New reactions of fluoroepoxides. Cleavage by trialkyl phosphites

1,1,3,3,3-Pentafluoro-2-pentafluorophenylpropene oxide. Precursor for novel phosphonates and ylides

“…The NMR data of the ylide [1,4,9] and the phosphonates [1,2] [7] were prepared according to literature procedures. …”

“…Epoxides of a few terminal perfluoroolefins CF 3 under C-C and C-O bond cleavage to give the ylides CF 3 (R 1 )C‫ס‬P(OR 2 ) 3 and decomposition products of the thermally unstable phosphorane intermediate FC(O)P(F)(OR 2 ) 3 , namely, difluorophosphoranes F 2 P(OR 2 ) 3 and carbon monoxide [1]. Diethyl trimethylsilyl phosphite, Me 3 SiOP(OEt) 2 , and perfluoroisobutene oxide gave fluorotrimethylsilane, the fluorophosphate FP(O)(OEt) 2 , and the perfluorovinyl phosphonate CF 2 ‫ס‬C(CF 3 )P(O)(OEt) 2 , which could be prepared by different routes [2,3].…”

Recent Advances in the Synthesis and Transformation of Carbamoyl Fluorides, Fluoroformates, and Their Analogues

“…The degradation of fluorine‐containing α‐oxides with phosphites through cleavage of the C−C and C−O bonds in epoxide ring was explored by Kadyrov et al [88] . The authors disclosed that reaction of perfluoroisobutene oxide ( 304 ) with trialkyl phosphites ( 305 ) under mild conditions afforded isopropylidene trialkoxy phosphoranes ( 306 ) and fluorocarbonyl trialkoxy fluorophosphoranes ( 307 ) (Scheme 56).…”

“…The authors disclosed that reaction of perfluoroisobutene oxide ( 304 ) with trialkyl phosphites ( 305 ) under mild conditions afforded isopropylidene trialkoxy phosphoranes ( 306 ) and fluorocarbonyl trialkoxy fluorophosphoranes ( 307 ) (Scheme 56). 307 was unstable and decomposed rapidly at room temperature to form trialkoxy difluorophosphorane ( 311 ) with evolving CO [88] . It was proposed that the first step in this reaction is the nucleophilic attack by trialkyl phosphite ( 305 ) on the carbon atom of the epoxide ring leading to a bipolar intermediate ( 308 ), which migrates a fluorine atom from the carbon to the phosphorus atom yielding a carbonyl fluoride ( 309 ) (Scheme 56).…”

“…It was proposed that the first step in this reaction is the nucleophilic attack by trialkyl phosphite ( 305 ) on the carbon atom of the epoxide ring leading to a bipolar intermediate ( 308 ), which migrates a fluorine atom from the carbon to the phosphorus atom yielding a carbonyl fluoride ( 309 ) (Scheme 56). Interaction of 309 with a second molecule of 305 followed by fluoride migration and the C−C bond fragmentation gives the final products ( 306 and 307 ) [88] . The formation of fluorocarbonyl trialkoxy fluorophosphorane ( 307 ) as an intermediate was also assumed in the reactions of trialkyl phosphite with carbamoyl fluoride and carbonic difluoride [14a] …”