Secondary and Tertiary Amines from Azo Compounds

Emerson, William S.; Reed, Sherman; Merner, R. R.

doi:10.1021/ja01848a030

Cited by 8 publications

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“…The corresponding secondary amines were formed in good to very high yields (31–96%). One year later, Emerson, Reed, and Merner prepared three alkylanilines in yields of 49–74% by treating an alcoholic solution of azobenzene and an aldehyde with 3.1 bar hydrogen in the presence of Raney Ni and sodium acetate (Scheme B) . In 1942, Henze and Humphreys developed a simple and rapid method for the synthesis of secondary aliphatic amines.…”

Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 94%

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

2020

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The reductive amination, the reaction of an aldehyde or a ketone with ammonia or an amine in the presence of a reducing agent and often a catalyst, is an important amine synthesis and has been intensively investigated in academia and industry for a century. Besides aldehydes, ketones, or amines, starting materials have been used that can be converted into an aldehyde or ketone (for instance, carboxylic acids or organic carbonate or nitriles) or into an amine (for instance, a nitro compound) in the presence of the same reducing agent and catalyst. Mechanistically, the reaction starts with a condensation step during which the carbonyl compound reacts with ammonia or an amine, forming the corresponding imine followed by the reduction of the imine to the alkyl amine product. Many of these reduction steps require the presence of a catalyst to activate the reducing agent. The reductive amination is impressive with regard to the product scope since primary, secondary, and tertiary alkyl amines are accessible and hydrogen is the most attractive reducing agent, especially if large-scale product formation is an issue, since hydrogen is inexpensive and abundantly available. Alkyl amines are intensively produced and use fine and bulk chemicals. They are key functional groups in many pharmaceuticals, agro chemicals, or materials. In this review, we summarize the work published on reductive amination employing hydrogen as the reducing agent. No comprehensive review focusing on this subject has been published since 1948, albeit many interesting summaries dealing with one or the other aspect of reductive amination have appeared. Impressive progress in using catalysts based on earth-abundant metals, especially nanostructured heterogeneous catalysts, has been made during the early development of the field and in recent years.

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Section: Reductive Amination Using Heteregeneous Transition Metal Cat...mentioning

confidence: 94%

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

2020

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The Preparation of Amines by Reductive Alkylation

Emerson

2011

Organic Reactions

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Reductive alkylation is the term applied to the process of introducing alkyl groups into ammonia or primary or secondary amine by means of an aldehdye or ketone in the presence of a reducing agent. This chapter is limited to those reductive alkylations in which the reducing agent is hydrogen and a catalysts or nascent hydrogen, usually from a metal‐acid combination; most of these reductive alkylations have been carried out with hydrogen and a catalyst.

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Iron‐Catalyzed Direct Alkylamination of Phenols with O‐Benzoyl‐N‐alkylhydroxylamines under Mild Conditions

et al. 2016

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An ovel iron-catalyzed direct alkylamination reactiono fp henols hasb een achieved with Obenzoyl-N-alkylhydroxylamines as aminating agents. This protocol provides af acile access to N-alkyl-substituteda minophenols though ar adical reactionf rom phenols.T he catalytic direct alkylamination operates at room temperature without the need of any ligands and additives to affordt he desired productsw ith excellentr egioselectivity and functional group tolerance. 1 HNMR (400 MHz, CDCl 3 ): d = 8.11 (s,1 H), 7.75 (d, J = 8.8 Hz, 1H), 7.72 (d, J = 8.4 Hz,1 H), 7.56 (d, J = 8.8 Hz, 1H), 7.34 (t, J = 8.4 Hz, 1H), 7.20 (t, J = 8.4 Hz, 1H), 7.18 (d, J = 8.8 Hz, 1H), 3.18-3.21 (m, 4H), 1.35-1.47 (m, 2H), 1.14-1.29 (m, 6H), 0.75-0.79 (m, 6H); 13 CNMR (100 MHz, CDCl 3 ): d = 153.

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Secondary and Tertiary Amines from Azo Compounds

Cited by 8 publications

References 0 publications

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

The Preparation of Amines by Reductive Alkylation

Iron‐Catalyzed Direct Alkylamination of Phenols with O‐Benzoyl‐N‐alkylhydroxylamines under Mild Conditions

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