Chlorophosphines, rearrangements

The initial products from oximes and chlorophosphines rearrange readily to the 219 220... 

Phosphine-containing ally lie alcohols 301 undergo facile [2,3]-sigmatropic rearrangements with chlorophosphines, furnishing highly enantioenriched (dr 25 1) or enantiopure, crystalline diphosphine monoxides boranes 302, which were deprotected by treatment with DABCO with formation of 303. The configuration at the newly-formed stereocenter is opposite to that expected based on prior studies, and an ab initio computational evaluation of the possible transition states was performed to explain the stereochemical course of the reaction (Scheme 101) [199]. 

Aiming at bifunctionalized allenes, alkynols were phosphorylated with diphenyl-chlorophosphine. The resulting intermediate underwent a spontaneous [2,3]-sigma-tropic rearrangement in the presence of hydrochloric acid as catalyst to afford the corresponding allenyl phosphine oxide that was converted in two steps to the sulfonyl derivative (Scheme 17). ... 

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