Unexpected cleavage of 2-azido-2-(hydroxymethyl)oxetanes: conformation determines reaction pathway?
An unanticipated cleavage of 2-azido-2-(hydroxymethyl)oxetanes is reported. In attempts to oxidize the title oxetanyl alcohols to the corresponding carboxylic acids with RuO4, cleaved nitriles were formed as the sole isolable products, while a closely related tetrahydrofuran gave solely the expected carboxylic acid. Quantum chemical calculations suggest that the divergent outcomes are governed by conformational differences in the azidoalcohols.
Farber
Elisa
E
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, United States.
Herget
Jackson
J
Gascón
José A
JA
Howell
Amy R
AR
D001386:Azides / Q000737:chemistry*; D004988:Ethers, Cyclic / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011789:Quantum Theory
D001386:Azides; D004988:Ethers, Cyclic; C005287:oxetane