Mechanistic and Catalytic Studies of Reversible Covalent Bonding

在美国国家科学基金会化学结构、动力学和机理项目的支持下，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项目。四个现代化学领域目前正在开发动态共价键：超分子化学、动态组合化学（DCC）、有机催化和酶抑制。然而，在这些地区常规利用的动态反应是有限的。这是因为大多数可逆共价键反应的平衡速度非常慢，因此在一个不切实际的时间尺度上交换组分。我们的目标是扩大可行的可逆系统的数量。为了做到这一点，Anslyn团队将首先探索四种可逆共价反应的机制，利用他们小组最近在这一努力中取得的成功，最后设计催化方法来加速可逆共价交换。他们将针对的四个可逆反应是：硫醇共轭加成，缩醛形成，半胺醚形成和亚磷酸酯酯交换。了解这四种反应的机理和揭示它们的催化方法将对化学界产生广泛的影响，原因有二。首先，他们将创建可逆共价系统，其他研究人员可以直接用于他们自己的需要。其次，也许更重要的是，他们将展示一种揭示催化方法的方法，其他化学家也可以采用这种方法来实现他们的目标。除了科学进步之外，德克萨斯大学奥斯汀分校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，其中安斯林博士总是平行这个实验室的一部分，以补充他的NSF资助。这个实验室是由德州大学提供设备和资助的，因此NSF的资金被用来在一个真正以研究为导向的环境中教育化学大一学生。

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.