Catalytic Carbonyl Olefination with Ruthenium Complexes

描述（由申请人提供）： 烯烃复分解反应在有机合成和高分子化学中已成为一个越来越重要的催化过程。然而，烯烃和羰基化合物之间的类似催化过程发现的成功和应用少得多。温和的、原子经济的催化羰基烯化反应的发展将代表一个重大的进步，它为传统的化学计量方法如Wittig和Tebbe反应提供了替代方案。 在该提议中，将开发用于羰基烯烃化的新型钌（II）卡宾催化剂体系。研究将集中在一种新型的，高度亲核的钌卡宾的设计和优化的反应条件，以促进催化剂周转。这应该允许开发醛和其他羰基化合物的催化羰基烯烃化的分子内和分子间变体，其产生最少量的容易除去的副产物。

DESCRIPTION (provided by applicant): Olefin metathesis has become an increasingly important catalytic process in both synthetic organic and polymer chemistry. However, the analogous catalytic processes between olefins and carbonyls has found much less success and application. The development of a mild, atom economical catalytic carbonyl olefination would represent a major advance by providing alternatives to traditional stoichiometric methodologies like the Wittig and Tebbe reactions. In this proposal, a novel ruthenium(ll) carbene catalyst system for carbonyl olefination will be developed. Research will focus on the design of a novel, highly nucleophilic ruthenium carbene and optimization of the reaction conditions to facilitate catalyst turnover. This should allow for development of both an intra- and intermolecular variant of a catalytic carbonyl olefination for aldehydes and other carbonyls that produces a minimal amount of easily removed by-products.