Center for Insoluble Protein Structures, Department of Chemistry and Interdisciplinary Nanoscience Center, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
J Org Chem. 2012 Jul 20;77(14):5894-906. doi: 10.1021/jo300904z. Epub 2012 Jul 3.
A highly regioselective Rh(I)-catalyzed hydrosilylation of enamides is presented. This mild protocol allows access to a wide variety of different arylsilanes with substitution at the β-position of the enamide and functionalization on the alkyl chain tethered to the silane. This protocol is extended to include a sequential one-pot hydrosilylation. Using diphenylsilane as the appendage point, hydrosilylation of a protected allyl alcohol followed by hydrosilylation of an enamide generates a complex organosilane in one step. This highly convergent strategy to synthesize these functionalized systems now provides a way for the rapid assembly of a diverse collection of silane-based peptidomimetic analogues.
本文报道了一种高区域选择性的 Rh(I)催化的烯酰胺氢硅烷化反应。该温和的反应条件可以实现各种不同的芳基硅烷的合成，这些硅烷在烯酰胺的β位具有取代基，并且在与硅烷相连的烷基链上具有官能团。该方法还扩展到包括顺序的一锅法氢硅烷化反应。使用二苯硅烷作为附加点，对保护的烯丙醇进行氢硅烷化反应，然后对烯酰胺进行氢硅烷化反应，一步即可生成复杂的有机硅烷。这种高度收敛的合成这些功能化体系的策略为快速组装各种基于硅烷的肽模拟物提供了一种方法。
