N-tosyloxycarbamates as a source of metal nitrenes:: Rhodium-catalyzed C-H insertion and aziridination reactions
N-tosyloxycarbamates as a source of metal nitrenes:: Rhodium-catalyzed C-H insertion and aziridination reactions
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DOI：
10.1021/ja0552850
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发表时间：
2005-10-19
影响因子：
15
通讯作者：
Lectard, S
中科院分区：
文献类型：
--
作者：
Lebel, H;Huard, K;Lectard, S
研究了铑催化N-对甲苯磺酰氧基氨基甲酸酯分解生成金属氮烯的反应，这些氮烯可进行分子内C-H插入或氮杂环丙烷化反应。脂肪族N-甲苯磺酰氧基氨基甲酸酯通过插入苄基、叔和仲C−H键产生高产率和立体特异性的恶唑烷酮。与烯丙基N-甲苯磺酰氧基氨基甲酸酯发生分子内氮丙啶化，以产生作为单一非对映异构体的氮丙啶。该反应在室温下使用铑催化剂和过量的碳酸钾进行，并且不需要使用强氧化剂，例如高价碘试剂。一个铑氮烯物种大概涉及，因为这两个反应是立体有择的。
The rhodium-catalyzed decomposition ofN-tosyloxycarbamates to generate metal nitrenes which undergo intramolecular C−H insertion or aziridination reaction is described. AliphaticN-tosyloxycarbamates produce oxazolidinones with high yields and stereospecificity through insertion in benzylic, tertiary, and secondary C−H bonds. Intramolecular aziridination occurs with allylicN-tosyloxycarbamates to produce aziridines as single diastereomers. The reaction proceeds at room temperature using a rhodium catalyst and an excess of potassium carbonate and does not require the use of strong oxidant, such as hypervalent iodine reagents. A rhodium nitrene species is presumably involved, as both reactions are stereospecific.