1,6-Carbene Transfer: Gold-Catalyzed Oxidative Diyne Cyclizations

作者：Noesel Pascal; Comprido Laura Nunes dos Santos; Lauterbach Tobias; Rudolph Matthias; Rominger Frank; Hashmi A Stephen K^*

来源：Journal of the American Chemical Society, 2013, 135(41): 15662-15666.

DOI：10.1021/ja4085385

In the presence of a gold catalyst an unprecedented oxidative cyclization of diynes takes place. The reaction cascade is initiated by an oxygen transfer from a N-oxide onto a gold-activated alkyne. The formed alpha-oxo carbene is transferred across the second alkyne yielding a stabilized vinyl carbene/cation. Alkyl migration or sp(3)-CH insertion then terminates the catalytic cycle by formation of highly substituted functionalized indenones. A 1,6-carbene shift could be supported by the oxidation of the vinyl carbene. This protocol represents an attractive alternative which are based on the metal-catalyzed decomposition of hazardous, not easily accessible, diazo compounds. to procedures

• 出版日期2013-10-16