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Molecules. 2016 Oct 17;21(10). pii: E1371.

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

Author information

1
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 1, Murmanska Street, Kiev 02094, Ukraine. anastasik7@rambler.ru.
2
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 1, Murmanska Street, Kiev 02094, Ukraine. olegkol321@gmail.com.

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 of P-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- and 31Р-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 into trans-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.

KEYWORDS:

2-halo-1,2λ5-oxaphosphetanes; allylphosphonates; phosphorus ketenes; vinylphosphonates

PMID:
27763512
PMCID:
PMC6274043
DOI:
10.3390/molecules21101371
[Indexed for MEDLINE]
Free PMC Article

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