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Tandem Insertion–[1,3]‐Rearrangement: Highly Enantioselective Construction of α‐Aminoketones

Yushuang Chen, Yun Liu, Zhaojing Li, Shunxi Dong, Xiaohua Liu, Xiaoming Feng

2020Angewandte Chemie14 citationsDOI

Abstract

Abstract An enantioselective synthesis of α‐aminoketone derivatives were readily available through a tandem insertion–[1,3] O‐to‐C rearrangement reaction. The rhodium salt and chiral N , N ′‐dioxide‐indium(III) complex make up relay catalysis, which enables the O−H insertion of benzylic alcohols to N ‐sulfonyl‐1,2,3‐triazoles, and asymmetric [1,3]‐rearrangement of amino enol ether intermediates, subsequently. Preliminary mechanistic studies suggested that the [1,3] O‐to‐C rearrangement step proceeded through an ion pair pathway.

Topics & Concepts

Enantioselective synthesisChemistrySulfoniumRhodiumRearrangement reactionTandemStereochemistryCatalysisCope rearrangementCarroll rearrangementEtherMigratory insertionCombinatorial chemistryMedicinal chemistrySalt (chemistry)Claisen rearrangementOrganic chemistryMaterials scienceComposite materialSynthesis and Catalytic ReactionsAsymmetric Hydrogenation and CatalysisCyclopropane Reaction Mechanisms