Nitrosobenzene‐Enabled Chiral Phosphoric Acid Catalyzed Enantioselective Construction of Atropisomeric N‐Arylbenzimidazoles
- 23 September 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 60 (47), 24888-24893
- https://doi.org/10.1002/anie.202111251
Abstract
Described herein is an imidazole ring formation strategy for the synthesis of axially chiral N-arylbenzimidazoles by means of chiral phosphoric acid catalysis. Two sets of conditions were developed to transform two classes of 2-naphthylamine derivatives into structurally diverse N-arylbenzimidazole atropisomers with excellent chemo- and regioselectivity as well as high levels of enantiocontrol. It is worth reflecting on the unique roles played by the nitroso group in this domino reaction. It functions as a linchpin by first offering an electrophilic site (N) for the initial C-N bond formation while the resulting amine performs the nucleophilic addition to form the second C-N bond. Additionally, it could facilitate the final oxidative aromatization as an oxidant. The atropisomeric products could be conveniently elaborated to a series of axially chiral derivatives, enabling the exploitation of N-arylbenzimidazoles for their potential utilities in asymmetric catalysis.Funding Information
- National Natural Science Foundation of China (21672048, 21825105)
This publication has 73 references indexed in Scilit:
- Towards the Limit of Atropochiral Stability: H‐MIOP, an N‐Heterocyclic Carbene Precursor and Cationic Analogue of the H‐MOP LigandChemistry – A European Journal, 2011
- Chiral Brønsted Acid Catalyzed Enantioselective α-Aminoxylation of EnecarbamatesAngewandte Chemie, 2010
- Resolution of the Atropochiral Biminap Ligand and Applications in Asymmetric CatalysisChemistry – An Asian Journal, 2010
- Chiral Brønsted Acid-Catalyzed Enantioselective α-Hydroxylation of β-Dicarbonyl CompoundsJournal of the American Chemical Society, 2009
- Regio- and Enantioselective Direct Oxyamination Reaction of Aldehydes Catalyzed by α,α-Diphenylprolinol Trimethylsilyl EtherAngewandte Chemie, 2007
- Regio‐ and Enantioselective Direct Oxyamination Reaction of Aldehydes Catalyzed by α,α‐Diphenylprolinol Trimethylsilyl EtherAngewandte Chemie, 2007
- Highly Stereoselective Formal [3 + 3] Cycloaddition of Enals and Azomethine Imines Catalyzed by N-Heterocyclic CarbenesJournal of the American Chemical Society, 2007
- Direct Asymmetric Hydroxyamination Reaction Catalyzed by an Axially Chiral Secondary Amine CatalystJournal of the American Chemical Society, 2006
- Chiral Brønsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic ActivationJournal of the American Chemical Society, 2004
- Enantioselective Mannich‐Type Reaction Catalyzed by a Chiral Brønsted AcidAngewandte Chemie, 2004