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Selective α-Amination and α-Acylation of Esters and Amides via Dual Reactivity of O-Acylhydroxylamines Toward Zinc Enolates

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Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds

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Abstract

α-Amino carbonyl and 1,3-dicarbonyl compounds are highly desirable motifs in organic synthesis and are present in many pharmaceutically and biologically relevant molecules. Selective α-amination and α-acylation of esters and amides have been developed, employing O-acylhydroxylamines as a dually reactive aminating and acylating reagent. Treatment of zinc enolates with O-acylhydroxylamines provides solely 1,3-dicarbonyl compounds under mild conditions. Introduction of a copper catalyst into the system shifts the reactivity entirely, yielding a-amination products exclusively.

Portions of this chapter have been published: McDonald, S.L.; Wang, Q. “Selective α-amination and α-acylation of esters and amides via dual reactivity of O-acylhydroxylamines toward zinc enolates,” Chem. Commun. 2014, 50, 2535–2538.

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  1. Department of Chemistry, Duke University, Durham, NC, USA

    Stacey L. McDonald

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McDonald, S.L. (2016). Selective α-Amination and α-Acylation of Esters and Amides via Dual Reactivity of O-Acylhydroxylamines Toward Zinc Enolates. In: Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-319-38878-6_2

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