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DOI: 10.1055/a-2785-2408
Catalytic Atroposelective aza-Grob Fragmentation: Unlocking a New Strategy for Axially Chiral Biarylnitriles
Authors
The authors are grateful for financial support from the National Key Research and Development Program of China (no. 2021YFA1500100) and the National Natural Science Foundation of China (22471254).
Supported by: National Key Research and Development Program of China 2021YFA1500100
Abstract
We report on the development of a catalytic atroposelective aza-Grob fragmentation of α-keto oxime esters—the first of its kind catalytic asymmetric version of this classical reaction. By leveraging torsional strain and multiple hydrogen-bonding activation, a catalytic asymmetric addition, followed by a stereospecific carbon–carbon cleavage reaction was developed, delivering axially chiral biarylnitriles in high yield and enantioselectivity. In this Synpact article, we present the conceptual framework of the catalytic asymmetric aza-Grob fragmentation and highlight the key structural features that enable atroposelective C–C bond scission.
Keywords
Atropisomers - Aza-Grob fragmentation - Axially chiral biaryls - Torsional strain - OrganocatalysisPublication History
Received: 07 December 2025
Accepted after revision: 09 January 2026
Article published online:
26 February 2026
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