Catalytic Carbonyl Olefination with Ruthenium Complexes

描述(由申请人提供)： 在合成有机化学和聚合物化学中，烯烃歧化反应已成为一个日益重要的催化过程。然而，烯烃和羰基之间的类似催化过程的成功和应用要少得多。开发一种温和的、原子经济的催化羰基烯化反应将是一大进步，因为它可以替代传统的化学计量方法，如Wittig反应和Tebbe反应。 在这项建议中，将开发一种新型的用于羰基烯化反应的Ru(11)卡宾催化剂体系。研究重点将集中在设计一种新型的、高度亲核的鲁卡宾，并优化反应条件，以促进催化剂的循环。这应该允许开发一种分子内和分子间变体，用于醛和其他羰基的催化羰基烯化反应，产生最少量的容易去除的副产物。

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.