Innovative Tools for Chemical Synthesis: Cyclase-Inspired Catalysis, Shuttle Catalysis, and Tandem Catalysis

首席调查员/项目总监(最后、第一、中间)：董，Vy，M -- 项目摘要/摘要： 有机金属试剂和中间体的合成和实现已成为一种 是形成复杂治疗剂的基石。因此，开发新的方法来处理 以简单高效的方式获取这些中间体已成为合成技术的一大焦点 有机和有机金属群落。有机锌试剂已被证明是一种强有力的工具 复杂有机合成领域，如羰基加成、交叉偶联反应(Negeshi偶联)、 以及烯烃和炔烃的官能化。随着对这些重要的亲核试剂的需求变得越来越多 显然，化学家们已经找到了通过高效和可持续的方法来制造它们的方法。以前的工作 Knochel和Sato的研究表明，镍和钛催化剂可以有效地将烯烃转化为有机锌， 然而，他们的工作并没有强加立体化学选择性。我们的目标，如本文所述，是为了扩展 使用手性钛催化剂和手性钛以对映体方法使用钛催化生成有机锌 以简单、无偏的烯烃为起始原料。随着这些立体化学活性的形成 对于亲核试剂，我们的目标是将它们与二氧化碳偶联，使用与之前在 董氏课题组。利用简单和容易获得的起始材料以及更多的结构 获得这些物种的不同催化剂和底物可以改善获得有机锌的途径 中间体及其在合成复杂最终产品中的用途。

Principle Investigator/Program Director (Last, first, middle): Dong, Vy, M   Project Summary/Abstract: The synthesis and implementation of organometallic reagents and intermediates has become a cornerstone in the formation of complex therapeutic agents. Thus, the development of novel methods for accessing these intermediates in a simple and efficient manner has become a large focus of the synthetic organic and organometallic community. Organozinc reagents have shown themselves to be a powerful tool in complex organic synthesis in areas such as carbonyl addition, cross coupling reactions (Negeshi coupling), and functionalization of alkenes and alkynes. As the need for these important nucleophiles becomes more apparent, chemists have sought out ways to make them by efficient and sustainable methods. Previous work by Knochel and Sato has shown that nickel and titanium catalysts can convert olefins to organozincs efficiently, however their work does not impose stereochemical selectivity. Our goal, described herein, is to expand on the use of titanium catalysis to generate organozincs in an enantiopure method using chiral titanium catalysts and simple, unbiased olefins as starting materials. Following the formation of these stereochemically active nucleophiles, we aim to couple them with carbon dioxide using chemistry similar to previous studies in the Dong research group. Utilizing simple and readily available starting materials as well as more structurally diverse catalysts and substrates to gain access to these species could improve access to organozinc intermediates as well as their use in the synthesis of complex final products.