Anionic Telomerizations of Styrene with Butylamines

Asahara, Teruzo; Senō, Manabu; Tanaka, S.; Den, Norio

doi:10.1246/bcsj.42.1996

Cited by 14 publications

(2 citation statements)

References 2 publications

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“…In all cases the anti-Markovnikov product 1-amino-2-phenylethane is obtained. Precatalysts used include metallic sodium ,− sodium naphthalide or lithium amides; the latter can also be prepared in situ with butyllithium . Depending on the reaction conditions, primary amines react with one or two styrene molecules to give secondary or tertiary amines.…”

Section: Styrenesmentioning

confidence: 99%

Metal-Initiated Amination of Alkenes and Alkynes

1998

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ContentsI. Introduction 675 II. Mechanism and Coordination Chemistry 676 1. Activation of the Olefin 677 a. Stoichiometric Use of Transition Metals 677 b. Making the Reaction Catalytic 679 2. N−H Activation by Alkali Metals 680 3. Activation of the N−H Bond by Early Transition Metals, Lanthanides, and Actinides 681 4. Activation of the N−H Bond by Late Transition Metals 684 III. Synthetic Applications of Catalytic Aminations 686 1. Aminations Catalyzed by Zeolites 686 2. Aminations Assisted by Alkali Metals 686 a. Ethylene 686 b. Aliphatic Olefins 687 c. Styrenes 688 d. 1,3-Butadienes 689 3. Aminations Catalyzed by Transition Metals 690 a. Palladium-Catalyzed Aminations of Olefins 690 b. Other Catalytic Oxidative Aminations of Olefins 693 c. Amination of Allenes 693 d. Intramolecular Amination of Alkynes 694 e. Intramolecular Amination of Alkenes 695 f. Tandem Cyclization Reactions of Aminoalkynes and -alkenes 697 g. Intermolecular Hydroamination Reactions 698 IV. Summary and Conclusions 699 V. Acknowledgments 700 VI. References 700

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Section: Styrenesmentioning

confidence: 99%

Metal-Initiated Amination of Alkenes and Alkynes

1998

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“…1 shows that the reaction temperature has great influences upon the yields of N-2-phenylethyl-o-anisidine. From the reaction scheme described later, the yield of the products was primarily governed by the extent of reaction (2). The equilibrium of this initiation reaction shifts to the left side with an increase in temperature, because this coupling reaction must have a negative entropy of reaction, while the rate of the reaction (2) would increase with an increasing temperature.…”

Section: Reaction Of Styrene With Anisidines and Phenetidinesmentioning

confidence: 99%

Anionic Telomerizations V

Asahara

Senō

Tanaka

et al. 1971

Bull. Japan Petrol. Inst.

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Summary:Anionic reactions of styrene with o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine and p-phenetidine catalyzed by an alloy of sodium and potassium metals were investigated. Each of the amines reacted with styrene to give 1:1 addition product, which was identified as N-2-phenylethylamine by means of NMR spectra, IR spectra, vapor pressure osmometry etc. A plausible mechanism to explain the formation of addition products was proposed, and also the reactions were discussed from the standpoint of anionic telomerization.

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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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Anionic Telomerizations of Styrene with Butylamines

Cited by 14 publications

References 2 publications

Metal-Initiated Amination of Alkenes and Alkynes

Metal-Initiated Amination of Alkenes and Alkynes

Anionic Telomerizations V

Hydroamination of Alkenes

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