Catalytic, Enantioselective Syn-Oxyamination of Alkenes.

The chemo-, regio-, diastereo-, and enantioselective 1,2-oxyamination of alkenes using selenium(II/IV) catalysis with a chiral diselenide catalyst is reported. This method uses N-tosylamides to generate oxazoline products that are useful both as protected 1,2-amino alcohol motifs and as chiral ligands. The reaction proceeds in good yields with excellent enantio- and diastereoselectivity for a variety of alkenes and pendant functional groups such as sulfonamides, alkyl halides, and glycol-protected ketones. Furthermore, the rapid generation of oxazoline products is demonstrated in the expeditious assembly of chiral PHOX ligands as well as diversely protected amino alcohols.

Beyond osmium: progress in 1,2-amino oxygenation of alkenes, 1,3-dienes, alkynes, and allenes.

Olefin 1,2-difunctionalization has emerged as a popular strategy within modern synthetic chemistry for the synthesis of vicinal amino alcohols and derivatives. The advantage of this approach is the single-step simplicity for rapid diversification, feedstock nature of the olefin starting materials, and the possible modularity of the components. Although there is a vast number of possible iterations of 1,2-olefin difunctionalization, 1,2-amino oxygenation is of particular interest due to the prevalence of both oxygen and nitrogen within pharmaceuticals, natural products, agrochemicals, and synthetic ligands. The Sharpless amino hydroxylation provided seminal results in this field and displayed the value in achieving methods of this nature. However, a vast number of new and novel methods have emerged in recent decades. This review provides a comprehensive review of modern advances in accomplishing 1,2-amino oxygenation of alkenes, 1,3-dienes, alkynes, and allenes that move beyond osmium to a range of other transition metals and more modern strategies such as electrochemical, photochemical, and biochemical reactivity.

Copper-Catalyzed Modular Amino Oxygenation of Alkenes: Access to Diverse 1,2-Amino Oxygen-Containing Skeletons.

Copper-catalyzed alkene amino oxygenation reactions using O-acylhydroxylamines have been achieved for a rapid and modular access to diverse 1,2-amino oxygen-containing molecules. This transformation is applicable to the use of alcohols, carbonyls, oximes, and thio-carboxylic acids as nucleophiles on both terminal and internal alkenes. Mild reaction conditions tolerate a wide range of functional groups, including ether, ester, amide, carbamate, and halide. The reaction protocol allows for starting with free amines as the precursor of O-benzoylhydroxylamines to eliminate their isolation and purification, contributing to broader synthetic utilities. Mechanistic investigations reveal the amino oxygenation reactions may involve distinct pathways, depending on different oxygen nucleophiles.

Copper-Catalyzed Amino Lactonization and Amino Oxygenation of Alkenes Using O-Benzoylhydroxylamines.

A copper-catalyzed amino lactonization of unsaturated carboxylic acids has been achieved as well as the analogous intermolecular three-component amino oxygenation of olefins. The transformation features mild conditions and a remarkably broad substrate scope, offering a novel and efficient approach to construct a wide range of amino lactones as well as 1,2-amino alcohol derivatives. Mechanistic studies suggest that the reaction proceeds via a distinctive O-benzoylhydroxylamine-promoted electrophilic amination of alkenes.

Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines.

This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates.

Copper-Catalyzed 1,2-Amino Oxygenation of 1,3-Dienes: A Chemo-, Regio-, and Site-Selective Three-Component Reaction with O-Acylhydroxylamines and Carboxylic Acids.

A three-component reaction for 1,2-amino oxygenation of 1,3-dienes has been achieved using O-acyl hydroxylamines and carboxylic acids. The reaction occurs through copper-catalyzed amination of olefins followed by nucleophilic addition of carboxylic acids, offering high levels of chemo-, regio-, and site-selectivity. The method is effective for both terminal and internal 1,3-dienes, including those bearing multiple, unsymmetrical substituents. The amino oxygenation conditions also exhibited remarkable selectivity toward 1,3-dienes over alkenes, good tolerance of sensitive functional groups, and reliable scalability.

Direct and Selective 3-Amidation of Indoles Using Electrophilic N-[(Benzenesulfonyl)oxy]amides.

Selective C-H amidation of 1H-indoles at the C3 position is reported as a direct entry to biologically important 3-aminoindoles. This transformation is achieved using novel N-[(benzenesulfonyl)oxy]amides as electrophilic nitrogen agents in the presence of ZnCl2. Interestingly, analogous reactions in the absence of ZnCl2 resulted in the formation of indole aminal products.