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Abstract
The bicyclic hydridophosphorane 2 was shown to undergo alkoxylation reaction with a series of benzenesulfenic esters 3 to give the corresponding isolable alkoxyphosphoranes in preparatively useful amounts (72–89%). The reaction pathway is interpreted in terms of a two-step process: the first step involves formation of alkoxyphosphorane 4 and thiaphosphorane 5, the second step involves the reaction of 5 with alcohol, converting to 4.