Kolodiazhna Anastasy O, Kolodiazhnyi Oleg I
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 1, Murmanska Street, Kiev 02094, Ukraine.
Molecules. 2016 Oct 17;21(10):1371. doi: 10.3390/molecules21101371.
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 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-, C-, F- and Р-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 -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.
介绍了对四元 2-卤代-1,2λ⁵-氧杂磷杂环丁烷磷(V)杂环的研究结果。描述了通过卤代酰与羰基化合物反应制备 2-卤代-1,2λ⁵-氧杂磷杂环丁烷的方法。基于低温核磁共振研究，提出了叶立德与醛的异步[2+2]环加成反应机理。2-卤代-1,2λ⁵-氧杂磷杂环丁烷作为单独的化合物被分离出来，其结构通过¹H-、C-、F-和P-核磁共振光谱得到证实。这些化合物是制备各种其他方法难以获得的有机和有机磷化合物的便利试剂。综述了 2-卤代-1,2λ⁵-氧杂磷杂环丁烷的化学和物理性质。2-氯-1,2λ⁵-氧杂磷杂环丁烷根据α-碳原子上的取代基，重排形成 2-氯烷基膦酸酯或转化为磷酸化烯烃。分析了 2-卤代-1,2λ⁵-氧杂磷杂环丁烷的潜在合成应用。2-卤代-1,2λ⁵-氧杂磷杂环丁烷可以很容易地转化为各种烯基膦酸酯：烯丙基或乙烯基膦酸酯、磷酮烯、硫酮烯、酮亚胺。
