Elsevier

Tetrahedron Letters

Volume 38, Issue 4, 27 January 1997, Pages 551-554
Tetrahedron Letters

Synthesis and thermolysis of hexacoordinate 1,2-oxaphosphetanides

https://doi.org/10.1016/S0040-4039(96)02369-6Get rights and content

Abstract

β-Hydroxyalkylphosphoranes containing two Martin ligands were prepared by reduction of the corresponding phenylthiomethylphosphorane with lithium naphthalenide, followed by the reaction with carbonyl compounds. Treatment of the β-hydroxyalkylphosphoranes with KH in the presence of 18-crown-6 gave a mixture of stereoisomers of the corresponding hexacoordinate 1,2-oxaphosphetanides stable in solution at room temperature. Upon heating, the adducts of benzophenone derivatives gave the corresponding benzophenones, while a hexafluoroacetone adduct afforded the corresponding olefin.

The titled compounds synthesized as a mixture of stereoisomers underwent two types of thermal reactions depending on the substituents.

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      Naganuma reported a quantitative yield of HFIB by the thermolyses of pentacoordinate 1,2-oxasiletanides [24] (Scheme 13). Similarly, HFIB was isolated in moderate yield by the thermal reaction of a hexacoordinate 1,2-oxaphosphetanide [25] (Scheme 14). The pyrolysis of four-membered cyclic oxyphosphoranes yielded HFIB among other products [26,27] (Scheme 15).

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