Stereochemical features of the physical and chemical interactions of singlet oxygen with enecarbamates.
Stereochemical features of the physical and chemical interactions of singlet oxygen with enecarbamates.
复制标题
单线态氧与烯氨基甲酸酯的物理和化学相互作用的立体化学特征。
作者：
Thomas H. W. Poon;N. Turro;Jessica R. Chapman;P. Lakshminarasimhan;X. Lei;S. Jockusch;Roberto Franz;I. Washington;W. Adam*;Sara G. Bosio
恶唑烷酮取代的氨基甲酸酯类化合物是研究(1)O(2)[2+2]和烯反应中立体电子、空间和构象对立体选择性和模式选择性影响的富含机械力的体系。这些烯氨基甲酸酯与(1)O(2)光氧化生成非对映异构体纯的二氧杂环己烷，分解生成恶唑烷酮甲醛和甲基脱氧安息香对映体过剩的两个对映体之一。立体选择性起源于烯丙基立体中心，这一结果得到了猝灭研究、计算分析和氚溶剂同位素效应的支持。[反应：见正文]
Oxazolidinone-substituted enecarbamates represent a mechanistically rich system for the study of stereoelectronic, steric, and conformational effects on stereoselectivity and mode selectivity in (1)O(2) [2 + 2] and ene reactions. Photooxygenation of these enecarbamates with (1)O(2) leads to diastereomerically pure dioxetanes that decompose to yield an oxazolidinone carbaldehyde and one of the two enantiomers of methyldesoxybenzoin in enantiomeric excess. Stereoselectivity originates at the allylic stereocenter, a result supported by quenching studies, computational analysis, and deuterium solvent isotope effects. [reaction: see text]
影响因子：
16.6
作者：
Ben-Shabat, S;Itagaki, Y;Nakanishi, K
通讯作者：
Nakanishi, K