Directed, Regiocontrolled Hydroamination of Unactivated Alkenes via Protodepalladation

Gurak, John A.; Yang, Kin S.; Liu, Zhen; Engle, Keary M.

doi:10.1021/jacs.6b02718

Cited by 180 publications

(96 citation statements)

References 56 publications

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“…Metal-catalyzed hydrofunctionalization of readily available alkenes with nitrogen sources is one of the most efficient methods for the synthesis of nitrogen-containing molecules; however, to achieve the high regio-and enantioselectivities of this transformation is still a challenge ( Fig. 2a) [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] . Among several activation strategies for alkene hydroamination, metal-catalyzed hydrogen atom transfer (HAT) reaction exhibits great Markovnikov selectivity and chemoselectivity (Fig.…”

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confidence: 99%

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Shen

Chen

et al. 2020

Nat Commun

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Highly regio-and enantioselective intermolecular hydroamination of alkenes is a challenging process potentially leading to valuable chiral amines. Hydroamination of alkenes via metalcatalyzed hydrogen atom transfer (HAT) with good regioselectivity and functional group tolerance has been reported, however, high enantioselectivity has not been achieved due to the lack of suitable ligands. Here we report a ligand-promoted cobalt-catalyzed Markovnikovtype selective radical hydroamination of alkenes with diazo compounds. This operationally simple protocol uses unsymmetric NNN-tridentate (UNT) ligand, readily available alkenes and hydrosilanes to construct hydrazones with good functional group tolerance. The hydrazones can undergo nitrogen-nitrogen bond cleavage smoothly to deliver valuable amine derivatives. Additionally, asymmetric intermolecular hydroamination of unactivated aliphatic terminal alkenes using chiral N-imidazolinylphenyl 8-aminoquinoline (IPAQ) ligands has also been achieved to afford chiral amine derivatives with good enantioselectivities.

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confidence: 99%

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Shen

Chen

et al. 2020

Nat Commun

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“… 17 – 20 Alternatively, proximal Lewis basic groups can direct functionalization of the alkene to afford the favored metallacycle ( Figure 1b ). 21 – 27 Finally, in stoichiometric investigations, the combination of a palladate complex and sterically hindered amine nucleophiles, promoted a trans -aminopalladation to functionalize the terminal carbon and produce the anti-Markovnikov constitutional isomer ( Figure 1c ). 28 , 29 However, conditions that afford the anti-Markovnikov aza-Wacker product, with simple aliphatic alkenes, have not been reported in catalytic amination reactions.…”

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Palladium-catalysed anti-Markovnikov selective oxidative amination

et al. 2018

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In recent years the synthesis of amines and other nitrogen containing motifs has been a major area of research in organic chemistry due to their being widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a Pd-catalyzed oxidative amination reaction, where the addition of the nitrogen occurs at the less substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide via trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favored products. Both the scope of the transformation and mechanistic investigations are reported.

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“…Early transition metals, such as Ti or Zr, as well as lanthanides, display high activity [9][10][11][12][13][14], although they are poorly stable, owing to their oxophilicity that renders them air and moisture sensitive. Late transition metals [3,[15][16][17][18][19]] feature a superior stability to moisture and air, together with broader functional group tolerance. Remarkably, cationic gold-based catalysts were highly active in the hydroamination of alkynes with amines [20,21].…”

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confidence: 99%

PdI2 as a Simple and Efficient Catalyst for the Hydroamination of Arylacetylenes with Anilines

et al. 2020

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The hydroamination reaction is a convenient alternative strategy for the formation of C–N bonds. Herein, we report a new versatile and convenient protocol for the hydroamination of arylacetylenes with anilines using palladium iodide in the absence of any added ligand as catalyst. Mild conditions, excellent regio- and stereoselectivity, and high functional group tolerance are the main features of this methodology. A subsequent reduction step gives access to a wide variety of secondary aromatic amines.

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Directed, Regiocontrolled Hydroamination of Unactivated Alkenes via Protodepalladation

Cited by 180 publications

References 56 publications

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Palladium-catalysed anti-Markovnikov selective oxidative amination

PdI2 as a Simple and Efficient Catalyst for the Hydroamination of Arylacetylenes with Anilines

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