N-Sulfonyltriazoles as Carbene Precursors

 描述(由申请人提供)：该研究计划的中心目标是开发新的战略反应，这些反应将在有机合成和用于合成新药物的方法方面产生广泛影响。特别强调的领域将是含有给体和受体基团的铑稳定的卡宾类化合物，它们能够进行一系列合成有用的转化。这些卡宾的化学成分异常丰富，并导致了几个新的合成战略反应。为了充分发展这一化学，有必要扩大可利用的捐助群体的范围。传统的方法是通过重氮化合物来获得给体/受体卡宾，这将给体基团的类型限制为芳基、杂芳基和一些烯基衍生物。在这项提案中，重点是使用N-磺酰基三氮唑来扩大给体/受体卡宾的范围，并特别强调开发氨基和烷氧基取代的卡宾衍生物。预计这些研究将导致新的合成方法的开发，这些方法不同于现有的从重氮乙酸酯衍生的罗卡宾的合成方法。这些方法将通过它们在生物相关的天然产物和重要的药物支架的合成中的应用来展示。

 DESCRIPTION (provided by applicant): The central goal of this research program is to develop new strategic reactions that will have broad impact in organic synthesis and on the methods used for the synthesis of new pharmaceutical agents. The particular area of emphasis will be on rhodium- stabilized carbenoids containing both donor and acceptor groups, which are capable of a range of synthetically useful transformations. The chemistry of these carbenoids is unusually rich and has resulted in several new strategic reactions for synthesis. In order to develop this chemistry fully it will be necessary to expand the range of donor groups that can be used. The traditional approach to the donor/acceptor carbenes is from diazo compounds, and this limits the type of donor groups to aryl, heteroaryl, and some alkenyl derivatives. In this proposal focuses on the use of N-sulfonyltriazoles to broaden the scope of donor/acceptor carbenes with a particular emphasis on the development of amino- and alkoxy substituted carbene derivatives. It is projected that these studies will result in the development of new synthetic methods that are distinct from those possible with the established rhodium carbenes derived from diazoacetates. These methods will be showcased by their use in the synthesis of biologically relevant natural products and important pharmaceutical drug scaffolds.