Stereochemisch definierte Osmium‐Zentren durch asymmetrische Diaminierung von Olefinen: Konsequenzen für den Mechanismus Osmium‐vermittelter Acrylester‐Oxidationen

Vicinal diamines are ubiquitous materials in organic and medicinal chemistry. The direct coupling of olefins and amines would be an ideal approach to construct these motifs. However, alkene diamination remains a long‐standing challenge in organic synthesis, especially when using two different amine components. We report a general strategy for the direct and selective assembly of vicinal 1,2‐diamines using readily available olefin and amine building blocks. This mild and straightforward approach involves in situ formation and photoinduced activation of N‐chloroamines to give aminium radicals that enable efficient alkene aminochlorination. Owing to the ambiphilic nature of the β‐chloroamines produced, conversion into tetra‐alkyl aziridinium ions was possible, thus enabling diamination by regioselective ring‐opening with primary or secondary amines. This strategy streamlines the preparation of vicinal diamines from multistep sequences to a single chemical transformation.

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Photoinduced Olefin Diamination with Alkylamines

Govaerts

Angelini

Hampton

et al. 2020

Angewandte Chemie

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Photoinduced Olefin Diamination with Alkylamines

et al. 2020

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Synthesis of Diamino Carboxylic Esters by Palladium‐Catalyzed Oxidative Intramolecular Diamination of Acrylates

Muñiz

Streuff

Chávez

et al. 2008

Chemistry An Asian Journal

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Unligated palladium(II) salts catalyze the oxidative diamination of acrylic esters to yield 2,3-diamino carboxylic esters. The reaction employs copper(II) bromide as oxidant and proceeds with good to excellent stereoselectivities and complete chemoselectivity. Preliminary mechanistic studies provide evidence for the involvement of a direct amination of the C--Pd bond in the alpha position relative to the ester group. This protocol significantly broadens the overall scope of the palladium-catalyzed diamination of alkenes and represents the first direct diamination of functionalized nonterminal substrates. The reaction yields readily protected 2,3-diamino acid derivatives, which can be considered as highly functionalized building blocks for subsequent synthesis. The use of one of these new diamination products as a suitable starting material in a short synthesis of the alkaloid absouline is demonstrated as an example.

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Stereochemisch definierte Osmium‐Zentren durch asymmetrische Diaminierung von Olefinen: Konsequenzen für den Mechanismus Osmium‐vermittelter Acrylester‐Oxidationen

Cited by 12 publications

References 41 publications

Photoinduced Olefin Diamination with Alkylamines

Photoinduced Olefin Diamination with Alkylamines

Photoinduced Olefin Diamination with Alkylamines

Synthesis of Diamino Carboxylic Esters by Palladium‐Catalyzed Oxidative Intramolecular Diamination of Acrylates

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