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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Synthesis and reactivity of alkyl-1,1,1-trisphosphonate esters
Jacqueline P Smits1, David F Wiemer
1Department of Chemistry, University of Iowa, Iowa City, Iowa 52242-1294, United States.
Abstract:
The α-trisphosphonic acid esters provide a unique spatial arrangement of three phosphonate groups and may represent an attractive motif for inhibitors of enzymes that utilize di- or triphosphate substrates. To advance studies of this unique functionality, a general route to alkyl derivatives of the parent system (R = H) has been developed. A set of new α-alkyl-1,1,1-trisphosphonate esters has been prepared through phosphinylation and subsequent oxidation of tetraethyl alkylbisphosphonates, and the reactivity of these new compounds has been studied in representative reactions that afford additional examples of this functionality.
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The reaction requires two equivalents of the Grignard reagent and introduces two identical alkyl groups, derived from the Grignard reagent, bonded to the hydroxyl-bearing carbon of the alcohol.
The reaction follows the typical nucleophilic acyl substitution mechanism. The Grignard...
