Benda Meghan C, France Stefan
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
Org Biomol Chem. 2020 Oct 7;18(38):7485-7513. doi: 10.1039/d0ob01742f.
Since the emergence of pseudo-C2-symmetric chiral phosphoric acids (CPA), much work has been done to utilize these systems in stereoselective, organocatalytic processes. Despite the success in this field, reasonably basic substrates such as imines are often required to achieve appreciable activation. In order to access a wider variety of potential reaction partners, many related organocatalysts with enhanced Brønsted acidity have since been developed. Chiral disulfonimides (DSIs) have materialized as one such powerful class of organocatalysts and have been shown to expand the list of potential substrates to include aldehydes and ketones via Brønsted, Lewis, or bifunctional acid activation. This versatility renders DSIs amenable to an impressive scope of reaction types, typically with remarkable stereoselectivity induced by asymmetric counteranion-directed catalysis (ACDC). This review serves to provide a complete analysis of the successful applications, mechanistic insights, and unmet challenges exhibited to date in DSI-catalyzed and -assisted processes.
自从伪C2对称手性磷酸（CPA）出现以来，人们开展了大量工作，以在立体选择性有机催化过程中利用这些体系。尽管该领域取得了成功，但通常需要诸如亚胺等具有一定碱性的底物才能实现可观的活化。为了获得更多种类的潜在反应伙伴，此后人们开发了许多具有增强布朗斯特酸度的相关有机催化剂。手性双磺酰亚胺（DSI）已成为一类如此强大的有机催化剂，并已证明通过布朗斯特、路易斯或双功能酸活化可将潜在底物范围扩大到包括醛和酮。这种多功能性使得DSI适用于令人印象深刻的一系列反应类型，通常在不对称抗衡离子导向催化（ACDC）的作用下具有显著的立体选择性。本综述旨在对DSI催化和辅助过程中迄今为止展示的成功应用、机理见解及未解决的挑战进行全面分析。
