Synthetic Utility of Silylene Transfer to Divinylketones

描述（由申请人提供）：亚甲硅烷基转移反应是允许立体特异性和立体选择性碳-碳键形成的强大转化。银催化的亚甲硅烷基转移到二乙烯基酮，然后用亲二烯体处理，允许非对映选择性地快速构建高度官能化的环己烯。这种两步，一锅反应允许快速进入高度取代的环己烯，可以作为合成生物活性天然产物的中间体。初步研究表明，金属催化剂是更密切地参与甲硅烷基转移比以前的理论。因此，金属催化剂上的手性配体具有允许对映选择性亚甲硅烷基转移的潜力。手性配体的加入将允许不仅是非对映选择性的，而且也是对映选择性的转化。这样，天然产物的合成可以实现对映体控制。从产生它们的生物体中分离出具有复杂生物活性的天然产物是很少令人担忧的。对这些化合物的生物学研究可能非常昂贵，这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，使它们在研究和潜在的医疗用途方面更具成本效益。

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.