Doi Ryusuke, Shibuya Masatoshi, Murayama Tsukasa, Yamamoto Yoshihiko, Iwabuchi Yoshiharu
†Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama 6-3, Sendai 980-8578, Japan.
‡Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.
J Org Chem. 2015 Jan 2;80(1):401-13. doi: 10.1021/jo502426p. Epub 2014 Dec 16.
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.
描述了1,5-二甲基-9-氮杂降冰片烷N-氧基（DMN-AZADO；1,5-二甲基-氮杂降冰片烷，2）作为一种在仲醇存在下选择性氧化伯醇的高效催化剂的开发。氮杂降冰片烷核的紧凑刚性结构赋予DMN-AZADO（2）强大的催化能力。多种受阻伯醇，如新戊基伯醇，能被DMN-AZADO（2）高效氧化为相应的醛，而仲醇保持不变。DMN-AZADO（2）在仲醇存在下将伯醇一锅氧化为相应羧酸以及二醇的氧化内酯化反应中也具有高催化效率。
