ChemInform Abstract: Iron-Catalyzed Sequential Reaction Towards α-Aminonitriles from Secondary Amines, Primary Alcohols and Trimethylsilyl Cyanide.

ChemInform ◽  
2016 ◽  
Vol 47 (24) ◽  
Author(s):  
Hang Shen ◽  
Liangzhen Hu ◽  
Qing Liu ◽  
Muhammad Ijaz Hussain ◽  
Jing Pan ◽  
...  
Keyword(s):  
Secondary Amines ◽  
Primary Alcohols ◽  
Sequential Reaction ◽  
Trimethylsilyl Cyanide

Iron-catalysed sequential reaction towards α-aminonitriles from secondary amines, primary alcohols and trimethylsilyl cyanide

2016 ◽  
Vol 52 (13) ◽  
pp. 2776-2779 ◽  
Author(s):  
Hang Shen ◽  
Liangzhen Hu ◽  
Qing Liu ◽  
Muhammad Ijaz Hussain ◽  
Jing Pan ◽  
...  
Keyword(s):  
Secondary Amines ◽  
Primary Alcohols ◽  
Reaction Conditions ◽  
One Pot ◽  
Sequential Reaction ◽  
Trimethylsilyl Cyanide

We developed a one-pot iron-catalysed sequential reaction of secondary amines under mild reaction conditions to give the corresponding α-aminonitriles.

Reactions of 4-phenyl-3H-1,2,4-triazole-3,5 (4H)-dione with alcohols and amines

1979 ◽  
Vol 57 (20) ◽  
pp. 2727-2733 ◽  
Author(s):  
Lê H. Dao ◽  
Donald Mackay
Keyword(s):  
Benzyl Alcohol ◽  
Title Compound ◽  
Secondary Amines ◽  
Secondary Alcohols ◽  
Bicyclic Compound ◽  
Tertiary Amines ◽  
Primary Alcohols ◽  
Complex Products ◽  
Diethyl Azodicarboxylate ◽  
Reaction Compound

Two equivalents of the title compound (1) react with one equivalent of primary alcohols to give good yields of nitrogen and 1-alkoxycarbonyl-2-N-phenylcarbamoyl-4-phenyl-1,2,4-triazolidine-3,5-di ones (3). With secondary alcohols or benzyl alcohol the major products are the ketone or benzaldehyde, while 3 are minor products. The latter can, however, be made the major products if pyridine is used to catalyze the reaction. Compound 3a dissociates on heating or in pyridine solution into the 1-methoxycarbonyltriazolidinedione 4.If alcohols are absent 1 is converted by pyridine or other tertiary amines into nitrogen and the bicyclic compound 9; if diethyl azodicarboxylate is present in the reaction compound 13 can be trapped.Primary and secondary amines react very rapidly with 1 to give nitrogen and complex products. It is likely that these are 1,2-dicarbamoyl-4-phenyltriazolidine diones, analogous to 3, and that they are very prone to dissociate in solution.

scholarly journals Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 140
Author(s):  
Dzmitry M. Zubrytski ◽  
Gábor Zoltán Elek ◽  
Margus Lopp ◽  
Dzmitry G. Kananovich
Keyword(s):  
Cyclic Peptide ◽  
Secondary Amines ◽  
Macrocyclic Lactones ◽  
Primary Alcohols ◽  
Diversity Oriented Synthesis ◽  
Bioactive Natural Products ◽  
Deacetylase Inhibitor ◽  
Synthetic Utility ◽  
Mixed Anhydrides ◽  
Last Stage

Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95−98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols). Intramolecular acylation yielding macrocyclic lactones can also be performed. The developed transformation has bolstered the synthetic utility of cyclopropanols as pluripotent intermediates in diversity-oriented synthesis of bioactive natural products and their synthetic congeners. For example, it was successfully applied for the last-stage modification of a cyclic peptide to produce a precursor of a known histone deacetylase inhibitor.

Best Synthetic Methods: Oxidation

2013 ◽  
Author(s):  
Douglass F. Taber
Keyword(s):  
Synthetic Methods ◽  
Secondary Amines ◽  
State University ◽  
Air Oxidation ◽  
Primary Alcohols ◽  
Ru Catalyst ◽  
Oxidation Of Alcohols ◽  
Aldehydes And Ketones ◽  
Diethyl Azodicarboxylate ◽  
The University

Karl A. Scheidt of Northwestern University described (Organic Lett. 2009, 11, 1651) the oxidation of primary alcohols such as 1 in the presence of an indole 2. The product 3, an active acylating agent, is readily converted to other esters and amides. K. Rajender Reddy of the Indian Institute of Chemical Technology, Hyderabad, developed (Tetrahedron Lett. 2009, 50, 2050) a protocol for the direct oxidation of a primary amine 4 to the corresponding nitrile 5. In the presence of ammonia, the same procedure converted aldehydes and primary alcohols into the nitriles. Several catalytic methods for the oxidation of alcohols to aldehydes and ketones have recently been put forward. René Grée of the Université de Rennes 1 found ( Tetrahedron Lett. 2009, 50, 1493) that ZnBr2 catalyzed the oxidation of alcohols with diethyl azodicarboxylate. Tsutomu Katsuki of Kyushu University designed (Tetrahedron Lett. 2009, 50, 3432) a Ru catalyst for the air oxidation of primary alcohols to aldehydes. Kazuaki Ishihara of Nagoya University showed (J. Am. Chem. Soc. 2009, 131, 251) that 1 mol % of 10 was sufficient to catalyze the oxidation of 6 to 7. With excess oxidant, 7 was carried on cleanly to 11. Nitroxyl radicals such as TEMPO have long been used to catalyze oxidations. Yoshiharu Iwabuchi of Tohoku University developed (J. Org. Chem. 2009, 74, 4619) a simple preparation of 13 , the most efficient such catalyst reported so far. This catalyst should also be useful for the oxidation reported by Professor Iwabuchi (Chem. Commun. 2009, 1739) of primary alcohols and aldehydes to the corresponding carboxylic acids. David S. Forbes of the University of South Alabama prepared (Tetrahedron Lett. 2009, 50, 1855) 16 by combining thioanisole with N-bromosuccinimide. The reagent 16 efficiently sulfenylated active methylene compounds. Jiri Srogl of the Academy of Sciences of the Czech Republic established (Organic Lett. 2009, 11, 843) conditions for the oxidation of primary and secondary amines to aldehydes and ketones. Olga A. Ivanova of Moscow State University demonstrated (Tetrahedron Lett. 2009, 50, 2793) that DMDO 21 could oxidize a sensitive amino cyclopropane such as 20 to the corresponding nitro compound.

Acceptorless amine dehydrogenation and transamination using Pd-doped layered double hydroxides

2018 ◽  
Author(s):  
Diana Ainembabazi ◽  
Nan An ◽  
Jinesh Manayil ◽  
Kare Wilson ◽  
Adam Lee ◽  
...  
Keyword(s):  
Layered Double Hydroxides ◽  
Oxidation States ◽  
Secondary Amines ◽  
Primary Amines ◽  
Acid Dissolution ◽  
Oxidative Amination ◽  
Strong Function ◽  
Excellent Activity ◽  
High Yields ◽  
Double Hydroxides

<div> <p>The synthesis, characterization, and activity of Pd-doped layered double hydroxides (Pd-LDHs) for for acceptorless amine dehydrogenation is reported. These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd species in 0, 2+, and 4+ oxidation states. Pd speciation and corresponding cataytic performance is a strong function of metal loading. Excellent activity is observed for the oxidative transamination of primary amines and acceptorless dehydrogenation of secondary amines to secondary imines using a low Pd loading (0.5 mol%), without the need for oxidants. N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, are dehydrogenated to the corresponding aromatics with high yields. The relative yields of secondary imines are proportional to the calculated free energy of reaction, while yields for oxidative amination correlate with the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative imine:amine selectivity. Poisoning tests evidence that Pd-LDHs operate heterogeneously, with negligible metal leaching; catalysts can be regenerated by acid dissolution and re-precipitation.</p> </div> <br>

A kinetic analysis of coupled sequential enzyme reactions

2018 ◽  
Author(s):  
Justin Eilertsen ◽  
Santiago Schnell
Keyword(s):  
Enzyme Assay ◽  
Sequential Reaction ◽  
Enzyme Reactions ◽  
Indicator Reaction ◽  
Single Substrate ◽  
Complex Sequences ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Single Enzyme

<div>As a case study, we consider a coupled enzyme assay of sequential enzyme reactions obeying the Michaelis--Menten reaction mechanism. The sequential reaction consists of a single-substrate, single-enzyme non-observable reaction followed by another single-substrate, single-enzyme observable reaction (indicator reaction). In this assay, the product of the non-observable reaction becomes the substrate of the indicator reaction. A mathematical analysis of the reaction kinetics is performed, and it is found that after an initial fast transient, the sequential reaction is described by a pair of interacting Michaelis--Menten equations. Timescales that approximate the respective lengths of the indicator and non-observable reactions, as well as conditions for the validity of the Michaelis--Menten equations are derived. The theory can be extended to deal with more complex sequences of enzyme catalyzed reactions.</div>

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