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CC BY 4.0 · Synthesis 2023; 55(16): 2427-2438
DOI: 10.1055/a-2039-5424
DOI: 10.1055/a-2039-5424
short review
Science of Synthesis Early Career Advisory Board
Synthetic Strategies to Control C–N Atropisomerism in Acyclic Amines and Amides
The authors gratefully acknowledge Newcastle University and the Royal Society (RGS\R1\221162) for funding.
Abstract
Atropisomeric molecules are a privileged class of stereogenic material that have important applications in catalysis, materials science and medicines. To date, the majority of work has been focused upon biaryl and heterobiaryl scaffolds involving restricted rotation between a pair of cyclic fragments, but C–N atropisomeric molecules based upon amines and amides, where the nitrogen atom is not part of a ring system, are rapidly emerging as an important class of stereogenic molecules. This is the focus of this Short Review, which begins by discussing the factors which influence the configurational stability of such molecules and provides a historical background to their synthesis. This is followed by a detailed discussion of state-of-the-art catalytic asymmetric strategies that are now available to access C–Nacyclic atropisomers including carboxamides, sulfonamides, sulfinamides, phosphamides and diarylamines. A variety of different synthetic approaches are discussed, including kinetic resolution/desymmetrization, amination, C–H functionalization, N-functionalization, and annulation.
1 Introduction
2 Atropisomerism in Acyclic Amines and Amides
3 Synthesis Directed by a Chiral Auxiliary
4 Atropselective Synthesis
4.1 Kinetic Resolution and Desymmetrization
4.2 Electrophilic Amination
4.3 C–H Functionalization
4.4 N-Functionalization
4.5 Annulation
5 Conclusions and Outlook
Key words
atropisomerism - axial chirality - amide - amine - asymmetric catalysis - anilide - stereoselectivityPublication History
Received: 27 January 2023
Accepted after revision: 20 February 2023
Accepted Manuscript online:
21 February 2023
Article published online:
06 June 2023
© 2023. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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For selected recent review articles, see:
For recent reviews on C–N atropisomerism, see:
For general reviews on medicinal applications, see:
Various elegant syntheses of C–C atropisomeric amides based upon hindered ortho-substituted benzamides have also been reported. For selected examples, see: