Imine Directed CpRh III -Catalyzed N-H Functionalization and Annulation with Amino Amides, Aldehydes, and Diazo Compounds

A multicomponent annulation that proceeds by imine directed Cp*Rh -catalyzed N-H functionalization is disclosed. The transformation affords piperazinones displaying a range of functionality and is the first example of transition metal-catalyzed multicomponent N-H functionalization. A broad range of...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 62; no. 1; p. e202210822
Main Authors Zoll, Adam J, Molas, Jenna C, Mercado, Brandon Q, Ellman, Jonathan A
Format Journal Article
LanguageEnglish
Published Germany 02.01.2023
Subjects
Aldehydes - chemistry
Amides
Azo Compounds
Catalysis
Imines
Rhodium - chemistry
Heterocycles
Multicomponent Reactions
Imine
N−H Functionalization
Rhodium
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Summary:A multicomponent annulation that proceeds by imine directed Cp*Rh -catalyzed N-H functionalization is disclosed. The transformation affords piperazinones displaying a range of functionality and is the first example of transition metal-catalyzed multicomponent N-H functionalization. A broad range of readily available α-amino amides, including those derived from glycine, α-substituted, and α,α-disubstituted amino acids, were effective inputs and enabled the incorporation of a variety of amino acid side chains with minimal racemization. Branched and unbranched alkyl aldehydes and various stabilized diazo compounds were also efficient reactants. The piperazinone products were further modified through efficient transformations. Mechanistic studies, including X-ray crystallographic characterization of a catalytically competent five-membered rhodacycle with imine and amide nitrogen chelation, provide support for the proposed mechanism.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202210822