Catalytic Atroposelective Dynamic Kinetic Resolution of Substituted Indoles

Abstract

Advances in asymmetric catalysis have led to enormous progress in the atroposelective synthesis of axially chiral biaryls. Because of the biological importance of indoles, stereogenic axes in aryl-substituted indoles have attracted considerable research attention in recent years. Here we present a summary of recent advances in the atroposelective synthesis of aryl-substituted indoles by dynamic kinetic resolution. Although several researchers have developed enantioselective syntheses of 3-arylindoles, N-arylindoles have been much less studied. Accordingly, we have developed a Pictet–Spengler reaction with catalytic and enantioselective control of the axial chirality around the C–N bond of the product. A chiral phosphoric acid induces the cyclization smoothly and with high yields and excellent enantioselectivities. To achieve this high selectivity, an NH group at the ortho-position of the N-substituted aromatic ring that interacts favorably with the catalyst is required. Furthermore, when substituted aldehydes are used instead of paraformaldehyde, both point and axial chiralities can be controlled during the cyclization.

1 Introduction

2 Atropisomerism in Indoles

3 Atroposelective Dynamic Kinetic Resolution of 3-Arylindoles

4 Atroposelective Dynamic Kinetic Resolution of N-Arylindoles

5 Conclusions

Key words

arylindoles - atropisomerism - chiral phosphoric acids - dynamic kinetic resolution - Pictet–Spengler cyclization

Publikationsverlauf

Eingereicht: 22. Oktober 2021

Angenommen nach Revision: 11. November 2021

Accepted Manuscript online:
11. November 2021

Artikel online veröffentlicht:
03. Dezember 2021

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