Institute for Organic Chemistry, Saarland University, Building C4.2, D-66123 Saarbruecken, Germany.
J Org Chem. 2013 Apr 5;78(7):3425-8. doi: 10.1021/jo4001349. Epub 2013 Mar 8.
σ-Alkyl iridium hydride complexes are generally postulated as intermediates in iridium-catalyzed hydrogenation. Fast reductive elimination results in the formation of the hydrogenation product. With an β-enamido ketone as unsaturated substrate, such an intermediate could be trapped because the semihydrogenated product coordinates trifold to the iridium, generating a stable 18e(-) complex, which does not eliminate.
σ-烷基铱氢化物配合物通常被认为是铱催化氢化反应的中间体。快速的还原消除导致氢化产物的形成。对于不饱和底物β-烯胺酮来说,这种中间体可以被捕获,因为半氢化产物以三倍配位的方式与铱配位,生成一个稳定的 18e(-)配合物,不会消除。