Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Abstract

Abstract:Results of research into four-membered 2-halo-1,2λ 5 -oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ 5 -oxaphosphetanes by reaction of P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-cycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ 5 -oxaphosphetanes were isolated as individual compounds and their structures were confirmed by 1 H-, 13 C-, 19 F-and 31 P-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halo-1,2λ 5 -oxaphosphetanes are reviewed. The 2-chloro-1,2λ 5 -oxaphosphetanes, rearrange with formation of 2-chloroalkyl-phosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ 5 -oxaphosphetanes are analyzed. The 2-halo-1,2λ 5 -oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl-or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.

Asymmetric electrophilic reactions in phosphorus chemistry

“…(93) (94) (95) The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisthiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation ( 96)) [130]. Under similar conditions, enantiomerically enriched (S)and (R)-O-isopropyl (R)-methylphosphinothioate stereospecifically reacted with diphenyl disulfide to form (S)-O-isopropyl S-phenyl (S)-methylphosphinodithioate with the same values of ees (Equation ( 97)) [129].…”

“…(96) (97) Chlorination of (S)-tert-butyl(phenyl)phosphine oxide with N-chlorosuccinimide yielded the (R)-tert-butyl(phenyl)phosphino chloride with retention of configuration, which, after treatment with phosphorus pentasulfide, was stereospecifically converted into (R)-tert-butyl(phenyl)phosphinoic chloride. The synthesis of optically active methyl (S)-tert-butyl(phenyl)phosphinodithioate, (S)-tert- (94) (92) (93) (94) (95) The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisthiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation ( 96)) [130]. Under similar conditions, enantiomerically enriched (S)and (R)-O-isopropyl (R)-methylphosphinothioate stereospecifically reacted with diphenyl disulfide to form (S)-O-isopropyl S-phenyl (S)-methylphosphinodithioate with the same values of ees (Equation ( 97)) [129].…”

“…Under similar conditions, enantiomerically enriched (S)-and (R)-O-isopropyl (R)-methylphosphinothioate stereospecifically reacted with diphenyl disulfide to form (S)-O-isopropyl S-phenyl (S)-methylphosphinodithioate with the same values of ees (Equation ( 97)) [128]. (92) (93) (94) (95) The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisdisulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation ( 96)) [130]. Under similar conditions, enantiomerically enriched (S)and (R)-O-isopropyl (R)-methylphosphinothioate stereospecifically reacted with diphenyl disulfide to form (S)-O-isopropyl S-phenyl (S)-methylphosphinodithioate with the same values of ees (Equation ( 97)) [129].…”

Asymmetric Electrophilic Reactions in Phosphorus Chemistry

“…The asymmetric induction in the case of the Appel and Atherton-Todd reactions was explained by the formation of long-lived phosphorane intermediate and Berry pseudorotation. The reaction mechanism was studied using theoretical calculations (Scheme 11) [95]. The reaction of tertiary alkylphosphines with donors of positive halogen leads to the formation of Phalogenylides [96][97][98].…”

“…The synthesis of optically active methyl (S)-tert-butyl(phenyl)phosphinodithioate, (S)-tert- The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisthiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation 96 Chlorination of (S)-tert-butyl(phenyl)phosphine oxide with N-chlorosuccinimide yielded the (R)-tert-butyl(phenyl)phosphino chloride with retention of configuration, which, after treatment with phosphorus pentasulfide, was stereospecifically converted into (R)-tert-butyl(phenyl)phosphinoic chloride. The synthesis of optically active methyl (S)-tert-butyl(phenyl)phosphinodithioate, (S)-tert- (95) The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bis-thiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation 96 The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisthiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation 96 Chlorination of (S)-tert-butyl(phenyl)phosphine oxide with N-chlorosuccinimide yielded the (R)-tert-butyl(phenyl)phosphino chloride with retention of configuration, which, after treatment with phosphorus pentasulfide, was stereospecifically converted into (R)-tert-butyl(phenyl)phosphinoic chloride. The synthesis of optically active methyl (S)-tert-butyl(phenyl)phosphinodithioate, (S)-tert- The treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bisthiophosphoryl disulfides under conditions of kinetically controlled resolution (reagent ratio 2:1) gave enantiomerically enriched tertiary phosphine oxides and phosphine sulfides with enantioselectivity 39% (Equation 96 Chlorination of (S)-tert-butyl(phenyl)phosphine oxide with N-chlorosuccinimide yielded the (R)-tert-butyl(phenyl)phosphino chloride with retention of configuration, which, after treatment with phosphorus pentasulfide, was stereospecifically converted into (R)-tert-butyl(phenyl)phosphinoic chloride.…”