New Approaches for Stereoselective Formation of Quaternary Carbon Stereocenters and Fragment Coupling

立体选择性形成季碳立构中心和片段偶联的新方法

• 批准号: 1265964
• 负责人: Larry Overman
• 金额: $ 62.99万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-07-01 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1265964&HistoricalAwards=false
• 关键词: New; Approaches; Stereoselective; Formation; Quaternary

With this award, the Chemistry Synthesis program is supporting the research of Professor Larry Overman of the University of California, Irvine. This project deals with a critical step in the efficient chemical synthesis of valuable, structurally complex, organic chemicals: the step that joins elaborate fragments. When the atoms joined in a fragment-coupling step are chiral, this union is particularly challenging. The objective of this research is the development and validation of new methods for combining complex fragments of this type. Specifically, the proposed research will investigate the general utility of bimolecular reactions of tertiary organometallic and tertiary carbon radicals with carbon-centered electrophiles for fragment coupling and the construction of quaternary-carbon stereocenters. Such chemical transformations are not currently part of the repertoire of organic synthesis, yet hold exciting potential to solve formidable challenges in constructing complex organic molecules. A majority of the synthesis methods under scrutiny will employ photo-redox catalysis, and, thus, are particularly attractive for their low environmental impact and their use of a sustainable energy source, visible light. Constructing complex carbon stereocenters remains today a hurdle to be surmounted in evolving efficient chemical syntheses of many organic molecules. The chemical syntheses to be developed should prove valuable in the discovery and potentially production of fine chemicals in the pharmaceutical, biotechnology, agricultural, and related industries. In addition, this program of research will lead to the training synthetic organic chemists at the BS, PhD and postdoctoral levels; such scientists play an essential role in the US pharmaceutical, biotechnology, agricultural, and chemical industries, besides being essential elements of university and college departments of chemistry and material science.

有了这个奖项，化学合成计划是支持教授拉里奥弗曼的加州大学欧文分校的研究。 该项目涉及有价值的，结构复杂的有机化学品的有效化学合成的关键步骤：连接精细片段的步骤。当在片段偶联步骤中连接的原子是手性的时，这种结合特别具有挑战性。本研究的目的是开发和验证用于组合这种类型的复杂片段的新方法。具体而言，拟议的研究将调查叔有机金属和叔碳自由基与碳中心亲电体的双分子反应的一般效用，用于片段偶联和季碳立体中心的构建。 这种化学转化目前还不是有机合成的一部分，但在解决构建复杂有机分子的艰巨挑战方面具有令人兴奋的潜力。大多数受审查的合成方法将采用光氧化还原催化，因此，由于其对环境的影响小和使用可持续能源可见光而特别有吸引力。构建复杂的碳立体中心今天仍然是许多有机分子的有效化学合成中需要克服的障碍。 待开发的化学合成应该证明在制药、生物技术、农业和相关工业中发现和潜在生产精细化学品方面是有价值的。此外，该研究计划将导致在BS，博士和博士后水平的合成有机化学家的培训;这些科学家在美国制药，生物技术，农业和化学工业中发挥着重要作用，除了是大学和学院化学和材料科学系的重要组成部分。