烯基氨基甲酸酯的立体选择性光氧化：臭氧与单线态氧的反应活性

Stereoselective photooxidation of enecarbamates: reactivity of ozone vs singlet oxygen.

作者信息

Sivaguru J, Saito Hideaki, Poon Thomas, Omonuwa Toma, Franz Roberto, Jockusch Steffen, Hooper Catherine, Inoue Yoshihisa, Adam Waldemar, Turro Nicholas J

机构信息

Department of Chemistry and Department of Chemical Engineering, Columbia University, 3000 Broadway, Mail Code 3119, New York, New York 10027, USA.

出版信息

Org Lett. 2005 May 26;7(11):2089-92. doi: 10.1021/ol0502230.

DOI:10.1021/ol0502230

PMID:15901141

Abstract

[reaction: see text]. Oxazolidinone-functionalized enecarbamates show contrasting behavior upon oxidation by singlet oxygen and by ozone. The observed stereoselectivity difference indicates that the oxidation with ozone is subject to classic steric effects, whereas the very high selectivity in the photooxidation with singlet oxygen is derived from vibrational deactivation.

摘要

[反应：见正文]。恶唑烷酮官能化的烯氨基甲酸酯在单线态氧和臭氧氧化时表现出截然不同的行为。观察到的立体选择性差异表明，臭氧氧化受经典空间效应的影响，而单线态氧光氧化中非常高的选择性源自振动失活。