Synthetic Utility of Silylene Transfer to Divinylketones

甲硅烷基转移至二乙烯基酮的合成应用

• 批准号: 7803595
• 负责人: CHRISTIAN C VENTOCILLA
• 金额: $ 1.44万
• 依托单位: UNIVERSITY OF CALIFORNIA-IRVINE
• 依托单位国家: 美国
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-04-15 至 2009-09-14
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7803595
• 关键词: 1,3-Butadiene; Alder plant; Biological; Biological Factors; Carbon; Complex; Cyclohexanes; Diels Alder reaction; Electrons; Ethers; Face; Hydrogenation; Ketones; Ligands; Medical; Metals; Methods; Names; Occupations; One-Step dentin bonding system; Organism; Reaction; Scheme; Silver; catalyst; cost effective; cyclohexene; diene; enol; galbanic acid; heme oxygenase-1; iridal; phomactin D; pi bond

DESCRIPTION (provided by applicant): Silylene transfer reactions are powerful transformations that allow for stereospecific and stereoselective carbon-carbon bond formations. Silver-catalyzed silylene transfer to divinyl ketones followed by treatment with a dienophile allows for the rapid construction of highly functionalized cyclohexenes diastereoselectively. This two-step, one-pot reaction allows for rapid entry into highly substituted cyclohexenes that could serve as intermediates in the synthesis of biologically-active natural products. Preliminary studies suggest that the metal catalyst is more intimately involved in the silylene transfer than previously theorized. Thus, chiral ligands on the metal catalyst carries the potential to allow enantioselective silylene transfer. The addition of chiral ligands would allow for the transformation to, not only be diastereoselctive, but enantioselective as well. In this way, the synthesis of natural products could be achieved with enantiocontrol. The isolation of complex biologically active natural products from the organisms that produce them is rarely feasable. Biological studies of such compounds could be very expensive depending on the method of isolaton or the organism from which they are isolated. It is the organic chemist's job to devise ways to synthesize these products so they are more cost effective to study and potentially be used for medical treatment.

描述（由申请人提供）：亚甲硅烷基转移反应是强大的转化，允许立体有择和立体选择性的碳-碳键形成。银催化的亚甲硅基转移到二乙烯基酮，然后用亲二烯体处理，可以快速非对映选择性地构建高度官能化的环己烯。这种两步一锅反应可以快速生成高度取代的环己烯，可以作为生物活性天然产物合成的中间体。初步研究表明，金属催化剂比之前的理论更密切地参与了硅烯转移。因此，金属催化剂上的手性配体具有允许对映选择性亚硅基转移的潜力。添加手性配体不仅可以实现非对映选择性，还可以实现对映选择性。这样，就可以实现对映体控制的天然产物的合成。从生产它们的生物体中分离复杂的生物活性天然产物很少可行。此类化合物的生物学研究可能非常昂贵，具体取决于分离方法或分离它们的生物体。有机化学家的工作是设计合成这些产品的方法，使它们的研究更具成本效益，并有可能用于医疗。