1,6-Carbene transfer: gold-catalyzed oxidative diyne cyclizations.
作者： Pascal Nösel , Laura Nunes dos Santos Comprido , Tobias Lauterbach , Matthias Rudolph , Frank Rominger
DOI: 10.1021/JA4085385
关键词: Catalytic cycle 、 Chemistry 、 Alkyne 、 Alkyl 、 Polymer chemistry 、 Carbene 、 Catalysis 、 Diazo 、 Oxidative phosphorylation 、 Photochemistry 、 Decomposition
摘要: In the presence of a gold catalyst an unprecedented oxidative cyclization diynes takes place. The reaction cascade is initiated by oxygen transfer from N-oxide onto gold-activated alkyne. formed α-oxo carbene transferred across second alkyne yielding stabilized vinyl carbene/cation. Alkyl migration or sp3-CH insertion then terminates catalytic cycle formation highly substituted functionalized indenones. A 1,6-carbene shift could be supported oxidation carbene. This protocol represents attractive alternative to procedures which are based on metal-catalyzed decomposition hazardous, not easily accessible, diazo compounds.
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