Bis- and tris-bicyclophosphites of D-glucofuranoside. Unexpected catalysis of P(III/V)-oxidation by triethylamine

The synthesis and characterization of several new bicyclophosphites via reactions of (i) ethyl 1-thi-alpha-D-glucofuranoside 3,5,6-phosphite with acid chlorides (phthalic or butylphosphoric), (ii) ethyl 1-thio-alpha-D-glucofuranosicle 3,5,6-phosphite with 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane and (iii) the tetraol system of ethyl 1-thio-alpha-D-glucofuranoside and hexaethyltriamidophosphite are reported. Unusual catalytic transformation of P(III)-compounds into the respective P(V)-spieces under extraordinary mild conditions by reaction with sulfur and selenium in the presence of triethylamine was discovered for the first time. (c) 2005 Elsevier Ltd. All rights reserved.