Carbonyl Phosphorylation via N,3E>-Bifunctional Reagents. Probing Mechanistic and Reactivity Features through Chemical and Isotopic Labelling

DOI: 10.1039/P19940003169

Source and publish data:

Journal of the Chemical Society. Perkin transactions I p. 3169 - 3182 (1994)

Update date:2022-08-05

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Authors:

Devitt, Paul G.

Kee, Terence P.

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Article abstract of DOI:10.1039/P19940003169

A range of organophosphorus(III) esters of the general form PX(SiR3)n has been prepared via reaction of PCl with R3SiOH or LiN(SiMe3)2 respectively.These esters will phosphonylate aldehydes via the Abramov reaction to afford α-siloxyphosphonate esters cleanly and in high yields.The mechanism of the Abramov reaction using POSiR3 reagents has been investigated by (i) 18O isotopic labelling experiments which reveal that reaction proceeds with exclusive rather than bond cleavage which, in turn, supports a mechanism with overall retention of configuration at phosphorus, (ii) double crossover experiments which support intramolecular silyl group transfer and (iii) manipulations of the electron-donating properties of the carbonyl substrate which suggest that bond formation is rate determining.Further tuning of the phosphonylation reaction is possible by manipulating (a) the nature of the phosphorus-coordinated donor atoms in the chelate ring, (b) the size and rigidity of the chelate ring, (c) the ester residue donor atom X and (d) the silicon substituents R.

Full text of DOI:10.1039/P19940003169

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