The C—F bond transformation of gem-difluorinated cyclopropanes without cleavage of the highly strained C—C bond is an intractable challenge. The synthesis of cyclopropanone ketals via double defluorination of gem-di...The C—F bond transformation of gem-difluorinated cyclopropanes without cleavage of the highly strained C—C bond is an intractable challenge. The synthesis of cyclopropanone ketals via double defluorination of gem-difluorinated cyclo-propanesunder transition-metal free and basic conditions has been developed. A broad range of gem-difluorinated cyclopro-panesand alcohols are amenable in present reaction to permit the synthesis of corresponding products in high yields. The reaction is elucidated to proceed via elimination and addition other than direct substitution based on the mechanistic studies. This transformation not only provides a new strategy for the construction of cyclopropanone ketals, but also reveals a new paradigm on C—F bond transformation without ring-opening of gem-difluorinated cyclopropanes.展开更多
β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·...β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·HF is described.This protocol provides a general and practical approach towards a wide variety ofβ-difluorinated alkyl bromides.Bothα-andβ-bromoalkyl alkenes are suitable substrates,leading to two distinct types of products.The extension of this protocol to vinyl chloride and iodide are also feasible.The synthetic versatility of this method has been highlighted by the late-stage modification of complex small molecules and further transformations of theβ-difluorinated alkyl halides to valuable CF_(2)-containing compounds.展开更多
A shelf-stable gem-difluorinated reagent β-tosyloxy-γ,γ-difluroallylboronic acid pinacol ester has been prepared, which can be easily used for the preparation of gem-difluorinated homoallylic alcohols through Brons...A shelf-stable gem-difluorinated reagent β-tosyloxy-γ,γ-difluroallylboronic acid pinacol ester has been prepared, which can be easily used for the preparation of gem-difluorinated homoallylic alcohols through Bronsted acid （PhCO2H） catalyzed gem-difluoroallylation of aldehydes and ketone.展开更多
文摘The C—F bond transformation of gem-difluorinated cyclopropanes without cleavage of the highly strained C—C bond is an intractable challenge. The synthesis of cyclopropanone ketals via double defluorination of gem-difluorinated cyclo-propanesunder transition-metal free and basic conditions has been developed. A broad range of gem-difluorinated cyclopro-panesand alcohols are amenable in present reaction to permit the synthesis of corresponding products in high yields. The reaction is elucidated to proceed via elimination and addition other than direct substitution based on the mechanistic studies. This transformation not only provides a new strategy for the construction of cyclopropanone ketals, but also reveals a new paradigm on C—F bond transformation without ring-opening of gem-difluorinated cyclopropanes.
基金This work was supported by the National Natural Science Foundation of China(21961047,21901266,21971261,22022114).
文摘β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·HF is described.This protocol provides a general and practical approach towards a wide variety ofβ-difluorinated alkyl bromides.Bothα-andβ-bromoalkyl alkenes are suitable substrates,leading to two distinct types of products.The extension of this protocol to vinyl chloride and iodide are also feasible.The synthetic versatility of this method has been highlighted by the late-stage modification of complex small molecules and further transformations of theβ-difluorinated alkyl halides to valuable CF_(2)-containing compounds.
文摘A shelf-stable gem-difluorinated reagent β-tosyloxy-γ,γ-difluroallylboronic acid pinacol ester has been prepared, which can be easily used for the preparation of gem-difluorinated homoallylic alcohols through Bronsted acid （PhCO2H） catalyzed gem-difluoroallylation of aldehydes and ketone.
