Catalytic Asymmetric Routes to Structurally Diverse P-Stereogenic Phosphines

有了这个奖项，美国国家科学基金会化学部的化学催化计划正在支持教授大卫S。达特茅斯学院的Glueck设计了制造手性膦的新方法。这些分子对于不对称催化是重要的，不对称催化在制药工业中用于制造具有高度特定形状的分子。目前制备手性膦的方法效率低，并且限于少量的起始原料。这些制造手性膦的障碍限制了至关重要的催化剂的发展。Glueck教授和他的研究小组正在开发催化剂，通过控制磷碳键的形成，可以从大量的起始材料中有效地制备手性膦。该项目还为研究生和本科生研究人员提供培训，并扩大代表性不足的群体，特别是美洲原住民在化学，教育和研究方面的参与。不对称过渡金属催化用于单一对映体药物的合成。手性非外消旋膦是这些催化剂的关键组分，但由于不对称膦合成的挑战而具有有限的结构多样性。由于不对称过渡金属催化剂的活性和选择性与手性膦的结构密切相关，因此制备这些分子的更好方法将支持新的过渡金属催化的不对称方法。Glueck教授和他的研究小组正在开发几种新的方法来制备手性非外消旋膦，包括：过渡金属催化的膦和双膦烷基化，以及磷杂环戊烷开环。还在探索研究，以了解这些转化中的动态和协同立体化学效应。更可持续的地球丰富的第一行过渡金属催化剂正在针对这些转换，以促进配体取代和周转。这些研究活动为不同的研究生和本科生群体提供了一个培训基地。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor David S. Glueck at Dartmouth College for designing new ways to make chiral phosphines. These molecules are important for asymmetric catalysis, which is employed in the pharmaceutical industry to make molecules with a highly specific shape used in pharmaceuticals. Current ways to prepare chiral phosphines are inefficient and limited to a small number of starting materials. These roadblocks to making chiral phosphines is a limitation to the development of critically important catalysts. Professor Glueck and his research group are developing catalysts that can efficiently make chiral phosphines from a large pool of starting materials by controlling the formation of phosphorous-carbon bonds. This project is also providing training for graduate and undergraduate researchers, as well as broadening the participation of underrepresented groups, especially Native Americans, in chemistry, education, and research. Asymmetric transition-metal catalysis is used for the synthesis of single-enantiomer drugs. Chiral non-racemic phosphines are key components of these catalysts but have limited structural diversity due to challenges with asymmetric phosphine synthesis. Since the activity and selectivity of the asymmetric transition metal catalysts are intimately linked to the structure of the chiral phosphines, better ways to make these molecules will support new transition metal catalyzed asymmetric processes. Professor Glueck and his research group are developing several new ways to prepare chiral non-racemic phosphines including: transition metal catalyzed phosphine and diphosphine alkylation, and phosphirane ring-opening. Studies to understand the dynamic and cooperative stereochemical effects in these transformations are also being explored. More sustainable earth-abundant first-row transition metal catalysts are being targeted for these transformations to facilitate ligand substitution and turnover. These research activities serve as a training ground for a diverse group of graduate and undergraduate students.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.