title: Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ⁵-oxaphosphetanes.
abstract: Results of research into four-membered 2-halo-1,2λ⁵-oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ⁵-oxaphosphetanes by reaction ofP-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ⁵-oxaphosphetanes were isolated as individual compounds and their structures were confirmed by ¹Н-,13C-,19F- and31Р-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-1,2λ⁵-oxaphosphetanes are reviewed. The 2-chloro-1,2λ⁵-oxaphosphetanes, rearrange with formation of 2-chloroalkyl-phosphonates or convert intotrans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ⁵-oxaphosphetanes are analyzed. The 2-halo-1,2λ⁵-oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl- or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.
authors.affiliation: Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 1, Murmanska Street, Kiev 02094, Ukraine. anastasik7@rambler.ru.
authors.forename: Anastasy O
authors.initials: AO
authors.lastname: Kolodiazhna
authors.affiliation: Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 1, Murmanska Street, Kiev 02094, Ukraine. olegkol321@gmail.com.
authors.forename: Oleg I
authors.initials: OI
authors.lastname: Kolodiazhnyi
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D061565:Cycloaddition Reaction; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000475:Alkenes; D006571:Heterocyclic Compounds; D009943:Organophosphorus Compounds; D002244:Carbon
keywords: 2-halo-1,2λ5-oxaphosphetanes; allylphosphonates; phosphorus ketenes; vinylphosphonates