title: Oxoammonium salt oxidations of alcohols in the presence of pyridine bases.
abstract: Oxoammonium salt oxidations (using 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) of alcohols containing a β-oxygen atom in the presence of pyridine yield dimeric esters, while in the presence of 2,6-lutidine the product is a simple aldehyde. The formation of a betaine between pyridine and an aldehyde is presented to explain this disparity in reactivity. The betaine is oxidized by the oxoammonium salt to give an N-acylpyridinium ion that serves as an acylating agent for ester formation. Steric effects deter the formation of such a betaine with 2,6-disubstituted pyridines. A series of alcohols containing a β-oxygen substituent were oxidized to aldehydes in the presence of 2,6-lutidine, and a short study of the relative reactivity of various alcohols is given. An overall mechanism for oxoammonium cation oxidations is suggested, premised on nucleophilic additions to the oxygen atom of the positively charged nitrogen-oxygen double bond. Possible mechanisms for both dimeric oxidations and simple oxidations are given.
authors.affiliation: Department of Chemistry, University of Connecticut , 55 North Eagleville Road, Storrs, Connecticut 06269-3060, United States.
authors.forename: James M
authors.initials: JM
authors.lastname: Bobbitt
authors.forename: Ashley L
authors.initials: AL
authors.lastname: Bartelson
authors.forename: William F
authors.initials: WF
authors.lastname: Bailey
authors.forename: Trevor A
authors.initials: TA
authors.lastname: Hamlin
authors.forename: Christopher B
authors.initials: CB
authors.lastname: Kelly
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002412:Cations / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D011726:Pyridinium Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D002412:Cations; D003497:Cyclic N-Oxides; D011725:Pyridines; D011726:Pyridinium Compounds; C003959:TEMPO