Nucleophilic transformations of cyclic phosphate triesters

Reactions of cyclic phosphate triesters, such as 2-ethoxy-1,3,2-dioxaphospholane 2-oxide, with Grignard reagents such as phenyl-, alkyl-, ethynyl-, and allyl-magnesium halides result in ring opening leading to the corresponding phosphonates, via nucleophilic attack of carbon on the phosphorus atom. Treatment of 2-ethoxy-1,3,2-dioxaphospholane 2-oxide with sodium borohydride yields ethyl 2-hydroxyethyl phosphite. This reaction is exclusive for the five-membered cyclic system: under these conditions acyclic phosphate triesters, such as triethyl phosphate, are unreactive and the analogous six-membered ring system, 2-ethoxy-1,3,2-dioxaphosphorinane 2-oxide reacts only partially to give unidentified phosphate esters and traces of phosphonate products. Both compounds were inert to NaBH4.