Cooperative Catalysis: Asymmetric Transformations with Unprotected Heteroatoms under Phase-Transfer Conditions

不对称相转移催化已成为一种不可或缺的合成工具，广泛应用于现代有机化学领域。它具有反应条件温和、大规模应用简单、反应体系对环境友好等优点，是可持续绿色化学领域的研究热点。然而，广泛的亲核原分子仍然存在，这不适合不对称相转移催化。该项目旨在通过开发一种新的方法来缩小这一广泛的范围，使配备无保护杂原子的底物的应用成为可能。为此目的，将实施合作催化方法。主要的想法是使用一种辅助催化剂，直接与亲核试剂配位来改变其性质，如酸性和反应性，并伴随形成阴离子络合物，以进一步与手性相转移催化剂相互作用。这种阴离子络合物的微调应该可以使其在各种有机转化中的应用成为可能。

Asymmetric phase-transfer catalysis has become an indispensable synthetic tool, widely established in the field of modern organic chemistry. Advantages such as the mild reaction conditions, simplified large-scale applications and the environmentally benign reaction systems render it as an attractive field with regards to sustainable green chemistry. Nevertheless, a broad range of pronucleophiles, improper for asymmetric phase-transfer catalysis, still exists. This project aims to shrink this broad range by the development of a novel method to render the application of substrates equipped with unprotected heteroatoms possible. For that purpose, a cooperative catalysis approach will be implemented. The major idea is to use a co-catalyst which directly coordinates the pronucleophile to modify its properties such as acidity and reactivity with a concomitant formation of an anionic complex for further interactions with the chiral phase-transfer catalyst. Fine-tuning of this anionic complex should render its application in miscellaneous organic transformations possible.