Sun Jianwei, Keller Valerie A, Meyer S Todd, Kozmin Sergey A
Department of Chemistry, University of Chicago, 5735 S. Ellis Ave, Chicago, IL 60637 Phone (+1)-773-7026886, Fax (+1)-773-7020805.
Adv Synth Catal. 2010 Mar 20;352(5). doi: 10.1002/adsc.200900835.
We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.
我们描述了一种使用富电子硅氧基炔烃的银催化羰基烯化反应的开发。该过程构成了三取代不饱和酯的有效合成方法,并且是广泛使用的霍纳 - 沃兹沃思 - 埃蒙斯反应的替代方法。使用1 - 硅氧基 - 1 - 丙炔或1 - 硅氧基 - 1 - 己炔时,一系列醛均表现出优异的非对映选择性。这种温和的催化过程还能在存在酯或酮官能团的情况下实现醛的化学选择性烯化。此外,由于不产生副产物,该催化过程非常适合开发可在单个烧瓶中进行的连续反应。