The development of 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO; 1,5-dimethyl-Nor-AZADO, 2) as an efficient catalyst for the selective oxidation of primary alcohols in the presence of secondary alcohols is described. The compact and rigid structure of the azanoradamantane nucleus confers potent catalytic ability to DMN-AZADO (2). A variety of hindered primary alcohols such as neopentyl primary alcohols were efficiently oxidized by DMN-AZADO (2) to the corresponding aldehydes, whereas secondary alcohols remained intact. DMN-AZADO (2) also has high catalytic efficiency for one-pot oxidation from primary alcohols to the corresponding carboxylic acids in the presence of secondary alcohols and for oxidative lactonization from diols.

The organocatalytic one-pot oxidative cleavage of terminal 1,2-diols to one-carbon-unit-shorter carboxylic acids is described. The combination of 1-Me-AZADO (cat.), NaOCl (cat.), and NaClO(2) caused smooth one-pot oxidative cleavage under mild conditions. A broad range of substrates including carbohydrates and N-protected amino diols were converted without epimerization. Terminal triols and tetraols respectively underwent cleavage of their C-2 and C-3 moieties to afford their corresponding two- and three-carbon-unit-shorter carboxylic acids.

Pyrolysis of bis(perfluoroalkanesulfonyl)bromonium ylides in various olefins results in highly stereospecific formation of cyclopropanes via unimolecular decomposition. Product analysis, kinetic study, substituent effects, and theoretical study revealed the generation of singlet bis(perfluoroalkanesulfonyl)carbenes stabilized by intramolecular coordination of sulfonyl oxygen.

Dehomologated Carboxylic Acids. -The reaction proceeds without epimerization of adjacent stereocenters and several functional groups such as triple bonds, acetonides, ethers, and carbamates are tolerated. Under these conditions, terminal triols and tetraols can also be converted into carboxylic acids. -(SHIBUYA*, M.; DOI, R.; SHIBUTA, T.; UESUGI, S.-I.; IWABUCHI, Y.; Org. Lett. 14 (2012) 19, 5006-5009, http://dx.

Development of an Azanoradamantane-Type Nitroxyl Radical Catalyst for Class--Selective Oxidation of Alcohols. -The title catalyst is prepared on gram scale in an eight-step sequence and affords superior results to TEMPO and its 1-methylazaadamantane analogue, not only for the class-selective oxidation of primary alcohols to aldehydes in the presence of a secondary alcohol, but also for the selective one-pot oxidation to carboxylic acids as well as for oxidative lactonization. -(DOI, R.; SHIBUYA, M.; MURAYAMA, T.; YAMAMOTO, Y.; IWABUCHI*, Y.; J. Org. Chem. 80 (2015) 1, 401-413, http://dx.