Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH

Giles, R.G.F.; O’Neill, Justin; Lee, Joo Ho; Chiu, Michael K.; Jung, Kyung Woon

doi:10.1016/j.tetlet.2013.05.101

Cited by 10 publications

(2 citation statements)

References 15 publications

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“…The combination of an NHC-amidate-alkoxide palladium catalyst with p -TsOH displays high catalytic activity toward intermolecular hydroamidation of vinyl arenes (Scheme ) . In comparison to the Brønsted acid-catalyzed hydroamidation of styrenes, this protocol efficiently suppresses the dimerization of the vinyl arene .…”

Section: Catalytic Addition Of Nitrogen Nucleophiles To Unconjugated ...mentioning

confidence: 99%

Late Transition Metal-Catalyzed Hydroamination and Hydroamidation

et al. 2015

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Section: Catalytic Addition Of Nitrogen Nucleophiles To Unconjugated ...mentioning

confidence: 99%

Late Transition Metal-Catalyzed Hydroamination and Hydroamidation

et al. 2015

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“…NMR、13 C NMR 和19 F NMR 均使用德国布鲁克公司 400 兆核磁共振仪(分别为 400, 100, 376 MHz).1 H NMR 的化学位移值以 TMS (δ 0.00)为标准确定,13 C NMR 的化学位移值以 CDCl 3 (δ 77.0)确定. 高分辨质谱是布鲁克公司 MicroTof-Q II mass spectrometer, 离子源为 ESI-TOF.…”

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Palladium-Catalyzed 5-exo-trig Hydroamidation of β,γ-Unsaturated Hydrazones for Synthesis of Dihydropyrazoles

Wang¹,

Chen²,

Zhang³

et al. 2020

Chin. J. Org. Chem.

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Hydroamination reaction is the addition of a N-H unit across the unsaturated C-C bond, which provides a convenient route for the formation of C-N bond. Considerable effort has been directed toward the development of multiple catalytic protocols for the hydroamination reaction in the past decades. Despite appreciable progress in this field, the development of general and practical strategy for the hydroamination of amides remains challenging, because the strong electron-withdrawing substituents (acyl, sulfonyl, or phosphinyl) strongly declined the nucleophilicity of the nitrogen. In this paper, a mild and efficient palladium-catalyzed 5-exo-trig hydroamidation of β,γ-unsaturated hydrazones for the synthesis of dihydropyrazoles has been developed. The reaction employs readily available starting materials, tolerates a wide range of functional groups, and produces a series of valuable dihydropyrazoles in good to high yields (63%～88%) under mild reaction conditions. Furthermore, a gram-scale hydroamidation of 1a afforded the dihydropyrazole 2a in 85% yield. In addition, the deuterium labeling experiment demonstrated that N-H is the hydrogen source in this hydroamidation process.

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Hydroamination of Alkenes

Reznichenko

Hultzsch

2015

Organic Reactions

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The addition of an amine NH‐functionality to alkenes (including vinyl arenes, conjugated dienes, allenes or ring‐strained alkenes), the so‐called hydroamination, represents a simple and highly atom‐economical approach for the synthesis of nitrogen‐containing products. A large variety of catalyst systems are available, ranging from alkali, alkaline earth, rare earth, Group 4 and Group 5 metals, to late transition metal catalysts, and, less prominent, Brønsted and Lewis acid‐based catalyst systems. The mode of operation of these catalyst systems can vary significantly and the different reaction mechanisms and the scope and limitations are discussed. While intramolecular hydroamination reactions can be readily achieved with a large number of catalyst systems, significantly fewer examples for the more challenging intermolecular hydroamination are known, especially for unactivated alkenes. The stereoselective hydroamination has also received significant attention due to the importance of chiral nitrogen‐containing molecules in pharmaceutical industry. A variety of highly selective chiral catalyst systems have been developed for intramolecular hydroaminations, while examples of intermolecular asymmetric hydroaminations are scarce. Hydroamination in the context of this review article is defined as the addition of HNR 2 across a non‐activated, unsaturated carbon‐carbon multiple bond. This review focuses on the hydroamination reaction of simple, non‐activated alkenes. The addition of amines to slightly activated alkenes, such as vinyl arenes, 1,3‐dienes, strained alkenes (norbornene derivatives, methylenecyclopropenes) and allenes is closely related and is covered as well. However, hydroamination reactions of alkynes and Aza‐Michael reactions involving the addition of an N‐H fragment across the conjugated or otherwise activated double bond of a Michael acceptor are not covered. The scope of amine types includes ammonia, primary and secondary aliphatic and aromatic amines, azoles, and hydrazines. N ‐Protected amines, such as ureas, carboxamides, and sulfonamides are covered as well, as they are important substrates for metal‐free and late transition metal‐based catalysts. The literature through January 2011 will be covered with two selected references from 2012 (comprising Table 3D). A supplemental reference list is provided for reports appearing February 2011 through April 2015. The chapter is organized by the nature of the carbon unsaturation to which the amine is added. Ranging from less reactive substrates such as ethylene and unactivated alkenes, to slightly activated substrates, such as vinyl arenes, and more activated substrates, including conjugated dienes, allenes and strained alkenes. Enantioselective hydroamination reactions, an area that has seen significant progress over the past decade, are discussed next. Finally, tandem hydroamination/carbocyclization reactions of aminodialkenes provide rapid access to complex alkaloidal skeletons. The tables at the end of the chapter are separated into five main sections: achiral intermolecular hydroamination, achiral intramolecular hydroamination, enantioselective intermolecular hydroamination, enantioselective intramolecular hydroamination, and tandem hydroamination/carbocyclization. Within the first four sections the tables are further divided into subsections based on the participating alkene, i.e. alkenes, vinyl arenes, dienes, allenes, and strained alkenes.

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Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH

Cited by 10 publications

References 15 publications

Late Transition Metal-Catalyzed Hydroamination and Hydroamidation

Late Transition Metal-Catalyzed Hydroamination and Hydroamidation

Palladium-Catalyzed 5-exo-trig Hydroamidation of β,γ-Unsaturated Hydrazones for Synthesis of Dihydropyrazoles

Hydroamination of Alkenes

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