Mechanistic and Catalytic Studies of Reversible Covalent Bonding

可逆共价键的机理和催化研究

• 批准号: 1212971
• 负责人: Eric Anslyn
• 金额: $ 40.5万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-07-15 至 2016-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1212971&HistoricalAwards=false
• 关键词: Mechanistic; Catalytic; Studies; Reversible; Covalent

With the support of the Chemical Structure, Dynamics, and Mechanism Program of the National Science Foundation, Professor Eric Anslyn of the University of Texas at Austin will lead a research program focused on dynamic covalent bonding. Four modern areas of chemistry are currently exploiting dynamic covalent bonding: supramolecular chemistry, Dynamic Combinatorial Chemistry (DCC), organocatalysis, and enzyme inhibition. However, the dynamic reactions routinely exploited in these areas are limited. This is due to the fact that most reactions involving reversible covalent bonding are very slow to equilibrate, and therefore exchange components on a time scale that is impractical. Our goal is to expand the number of reversible systems that are practical. To do this, the Anslyn team will first explore the mechanisms of four reversible covalent reactions, capitalize on successes that their group has recently had in this endeavor, and finally devise catalytic methods to speed up the reversible covalent interchange. The four reversible reactions they will target are: thiol conjugate addition, acetal formation, hemiaminal ether formation, and phosphinite transesterification. Understanding the mechanisms of these four reactions and uncovering methods for their catalysis will have a broad impact on the chemical community for two reasons. Firstly, they will create reversible covalent systems that other investigators can directly use for their own needs. Second, and maybe of even broader significance, they will demonstrate an approach for uncovering methods of catalysis that other chemists can also adopt for their goals. In addition to the scientific advances, the University of Texas (UT) at Austin offers a unique environment for broader impact. This University runs a Freshman Research Initiative (FRI) laboratory for undergraduates, wherein Dr. Anslyn always parallels a portion of this laboratory to complement his NSF funding. This laboratory is equipped and sponsored by UT, and thereby the NSF funding is leveraged to educate freshman chemistry students in a truly research oriented setting.

在国家科学基金会化学结构，动力学和机制计划的支持下，德克萨斯大学奥斯汀分校的Eric Anslyn教授将领导一个专注于动态共价键的研究计划。 四个现代化学领域目前正在利用动态共价键：超分子化学，动态组合化学（DCC），有机催化和酶抑制。 然而，在这些领域常规利用的动态反应是有限的。这是由于大多数涉及可逆共价键合的反应平衡非常缓慢，因此在不切实际的时间尺度上交换组分。我们的目标是扩大实用的可逆系统的数量。 为此，Anslyn团队将首先探索四种可逆共价反应的机制，利用他们团队最近在这奋进取得的成功，最后设计催化方法来加速可逆共价交换。 四个可逆反应，他们将目标是：硫醇共轭加成，缩醛形成，半缩醛胺醚形成，和次膦酸酯的酯交换。了解这四种反应的机理并揭示其催化方法将对化学界产生广泛的影响，原因有二。 首先，他们将创造可逆的共价体系，其他研究人员可以直接用于他们自己的需要。 第二，也许具有更广泛的意义，他们将展示一种方法来揭示催化方法，其他化学家也可以采用他们的目标。除了科学进步，德克萨斯大学奥斯汀分校（UT）还为更广泛的影响提供了独特的环境。 这所大学为本科生开设了一个新生研究计划（FRI）实验室，其中Anslyn博士总是平行于这个实验室的一部分，以补充他的NSF资金。 该实验室由UT提供设备和赞助，因此NSF的资金被用来在真正以研究为导向的环境中教育大一化学学生。