Intramolecular amine-induced [1,3]-sigmatropic rearrangement in the reactions of aminophosphinites or phosphites with elemental sulfur or selenium.

摘要: Ether- and thioether-functionalized cyclodiphosphazanes cis-[tBuNP(OCH2CH2EMe)]2 (E = O, 1; E S, 2) react with 2 equiv of elemental sulfur or selenium to produce dichalcogenides cis-[tBuNP(E)(OCH2CH2EMe)]2 (4−6), whereas the similar reaction amine-functionalized cyclodiphosphazane cis-[tBuNP(OCH2CH2NMe2)]2 (3) chalcogen results in formation thio- selenophosphates trans-[tBuNP(O)(ECH2CH2NMe2)]2 7; Se, 8) through [1,3]-sigmatropic rearrangement. The X-ray crystal structure 8 confirms rearranged product as trans isomer a planar P2N2 ring. equimolar P(OCH2CH2OMe)3 (9) produces simple sulfide selenide EP(OCH2CH2OMe)3 11; 12) derivatives, respectively. In contrast, between P(OCH2CH2NMe2)3 (10) S Se furnishes products (13 14). rearrangement was monitored by 31PNMR spectroscopy, which selenophosphinic acid ...