Regio- and Enantioselective Intermolecular Hydroacylation: Substrate-Directed Addition of Salicylaldehydes to Homoallylic Sulfides
Regio- and Enantioselective Intermolecular Hydroacylation: Substrate-Directed Addition of Salicylaldehydes to Homoallylic Sulfides
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DOI：
10.1021/ja107198e
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发表时间：
2010-11-24
影响因子：
15
通讯作者：
Dong, Vy M.
中科院分区：
文献类型：
--
作者：
Coulter, Matthew M.;Kou, Kevin G. M.;Dong, Vy M.
本文报道了一种在温和条件下铑催化的、区域选择性和对映选择性的烯烃分子间氢酰化反应。在螺环亚磷酰胺配体（R）-SIPHOS-PE存在下，含底物导向基团的高烯丙基硫醚与水杨醛衍生物发生加氢酰化反应，生成α-支化酮，选择性>20：1，ee值高达97%，1，2-二取代烯烃的不对称分子间加氢酰化反应也适用。
We report a Rh-catalyzed, regio- and enantioselective intermolecular olefin hydroacylation under mild conditions. Hydroacylations between homoallylic sulfides, containing a substrate-bound directing group, and salicylaldehyde derivatives occur in the presence of a spiro-phosphoramidite ligand, (R)-SIPHOS-PE, to give alpha-branched ketones in >20:1 selectivity and up to 97% ee. Our conditions are also applicable to the asymmetric intermolecular hydroacylation of 1,2-disubstituted olefins.