Department of Chemistry, The University of Liverpool, Crown Street, Liverpool L69 7ZD, UK.
J Am Chem Soc. 2012 Nov 28;134(47):19314-7. doi: 10.1021/ja306602g. Epub 2012 Nov 16.
A highly regio- and stereospecific rhodium-catalyzed allylic alkylation of tertiary allylic alcohol derivatives with a cyanohydrin pronucleophile is described. This direct and operationally simple protocol provides a fundamentally novel approach toward the synthesis of α-quaternary substituted ketones and circumvents many of the inherent problems associated with conventional enolate alkylation reactions. The stereospecific variant of this reaction provides the enantiomerically enriched α-quaternary substituted allylic aryl ketone, which is a particularly challenging intermediate for more conventional enolate-based strategies.
描述了一种高区域和立体选择性的铑催化的三级烯丙基醇衍生物与氰醇亲核试剂的烯丙基烷基化反应。这种直接且操作简单的方法为合成α-季碳取代的酮提供了一种全新的方法，同时避免了传统烯醇烷基化反应中存在的许多固有问题。该反应的立体特异性变体提供了对映体富集的α-季碳取代的烯丙基芳基酮，这是一种更传统的基于烯醇的策略特别具有挑战性的中间体。
