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

有了这个奖项，化学合成项目支持加州大学欧文分校的拉里·奥弗曼教授的研究。这个项目处理的是高效化学合成有价值的、结构复杂的有机化学品的关键步骤：连接复杂碎片的步骤。当在片段耦合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结合这类复杂片段的新方法。具体来说，本研究将探讨叔有机金属和叔碳自由基与碳中心亲电试剂的双分子反应在片段偶联和构建季碳立体中心方面的一般效用。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。审查中的大多数合成方法将采用光氧化还原催化，因此，它们对环境的影响小，并使用可持续的能源，可见光，特别有吸引力。构建复杂的碳立体中心仍然是当今许多有机分子的高效化学合成中需要克服的障碍。待开发的化学合成应证明对制药、生物技术、农业和相关工业中精细化学品的发现和潜在生产有价值。此外，该研究计划将导致培养学士，博士和博士后水平的合成有机化学家；这些科学家在美国的制药、生物技术、农业和化学工业中发挥着至关重要的作用，同时也是大学和学院化学和材料科学系的重要组成部分。

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.