The reaction of dithiadiphosphetane disulfides with dienes, alkenes and thioaldehydes

Synthesis, some properties and structural features of 1,2-thiaphosphacyclanes

“…An effective straightforward synthesis of fused 2-thioxo-1,2thiaphosphetanes has been proposed 58 based on the addition of dithiaphosphetane disulfides R 2 P 2 S 4 to sterically hindered alkenes. Thus exo-[2+2]-cycloaddition of R 2 P 2 S 4 to the multiple bond of norbornadiene (NBD) results in a series of stable tricyclic 2-thioxo-1,2-thiaphosphetanes 61.…”

“…The cycloaddition of Fc 2 P 2 S 4 to cyclohexene, norbornene and hexamethylbi- .0]hexa-2,5-diene was investigated. 58 As cyclohexene did not react with Fc 2 P 2 S 4 , the authors supposed that only sterically strained alkenes are able to react according to the cycloaddition scheme under such mild conditions giving products of the type 62.…”

“…It is interesting to note that with allowance for the difference in the chemical structure, i.e., with the presence of the sulfur atom in the ring, compound 15 is virtually isostructural with its precursor, methylidene(thioxo)phosphorane 14 Mes7P(S)=C(SiMe 3 ) 2 . 34 In the series of 1,2-thiaphosphetanes, the representatives of the smallest group of 1,2-thiaphosphacyclanes, only for two ferrocenyl-substituted thiophosphoryl compounds 61c and 62b 58,103 are X-ray data available. In these compounds, the four-membered ring is part of a fused cage system, both compounds being represented by exo-isomers.…”