Oxidative coupling of amines and carbon monoxide catalyzed by palladium complexes. Mono- and double carbonylation reactions promoted by iodine compounds

1990 ◽  
Vol 68 (9) ◽  
pp. 1544-1547 ◽  
Author(s):  
Ilan Pri-Bar ◽  
Howard Alper
Keyword(s):  
Carbon Monoxide ◽  
Oxidative Coupling ◽  
Room Temperature ◽  
Palladium Complexes ◽  
Secondary Amines ◽  
Primary Amines ◽  
Palladium Acetate ◽  
Principal Product ◽  
Iodine Compounds ◽  
Primary And Secondary Amines

Iodine is an effective promoter for the carbonylation of primary and secondary amines to ureas using palladium acetate as the catalyst and a base (e.g. K2CO3) in acetonitrile (3 h at 95 °C and 2.7 atm). Oxamides are formed in excellent yields when secondary amines are carbonylated in the presence of iodide ion and oxygen, while primary amines give ureas as the principal product at 95 °C, and oxamide at room temperature. Keywords: oxamides, ureas, double carbonylation, amines.

Alkene Difunctionalization Directed by Free Amines: Diamine Synthesis via Nickel-Catalyzed 1,2-Carboamination

2021 ◽  
Author(s):  
Taeho Kang ◽  
José Manuel González ◽  
Zi-Qi Li ◽  
Klement Foo ◽  
Peter Cheng ◽  
...  
Keyword(s):  
Nickel Catalyst ◽  
Room Temperature ◽  
Kinetic Studies ◽  
Fine Tuning ◽  
Secondary Amines ◽  
Protecting Group ◽  
Wide Range ◽  
Leaving Group ◽  
Primary And Secondary Amines ◽  
Reaction Proceeds

A versatile method to access differentially substituted 1,3- and 1,4-diamines via a nickel-catalyzed three-component 1,2-carboamination of alkenyl amines with aryl/alkenylboronic ester nucleophiles and N–O electrophiles is reported. The reaction proceeds efficiently with free primary and secondary amines without needing a directing auxiliary or protecting group, and is enabled by fine-tuning the leaving group on the N–O reagent. The transformation is highly regioselective and compatible with a wide range of coupling partners and alkenyl amine substrates, all performed at room temperature. A series of kinetic studies support a mechanism in which alkene coordination to the nickel catalyst is turnover-limiting.

Aroylacetylene Based Amino-Yne Click Polymerization toward Nitrogen Containing Polymers

2019 ◽  
Author(s):  
Xu Chen ◽  
Rong Hu ◽  
Bo Song ◽  
Anjun Qin ◽  
Ben Zhong Tang
Keyword(s):  
Room Temperature ◽  
Aqueous System ◽  
Secondary Amines ◽  
Primary Amines ◽  
Molecular Weights ◽  
Highly Efficient ◽  
Click Polymerization ◽  
Application Prospects

A highly efficient, spontaneous, and atom-economic polymerization of aroylacetylenes and amines at room temperature in air was established, and poly(<i>β</i>-enaminone)s with high molecular weights were produced in nearly quantitative yields. Moreover, singly <i>E</i>-configuration polymers can be obtained efficiently with secondary amines, while absolute <i>Z</i>-configuration products were prepared when using primary amines. In addition, the poly(<i>β</i>-enaminone)s can be degraded by primary amines in aqueous system to obtain definite compounds, proving their wide application prospects as degradable nitrogen containing polymers.

Reactions of Perimidin-4-ones and -6-ones with amines

1977 ◽  
Vol 30 (9) ◽  
pp. 2063 ◽  
Author(s):  
DW Cameron ◽  
EL Samuel
Keyword(s):  
Double Bond ◽  
Room Temperature ◽  
Significant Degree ◽  
Secondary Amines ◽  
Nucleophilic Attack ◽  
Side Chain ◽  
Amino Compounds ◽  
Primary And Secondary Amines ◽  
Benzenoid Ring

π-Deficient perimidin-4- and -6-one systems reacted readily with primary and secondary amines at room temperature. Nucleophilic attack occurred not only at the enone double bond, but also at positions 7 and 9 on the benzenoid ring. Highly coloured mono-, di- or tri-aminated derivatives were thereby obtained. A significant degree of bond fixation was indicated. Side-chain amination of 9-methyl substituents was observed, analogous to processes encountered in quinone chemistry. On continued contact with amine the products were converted partly into 9-formyl derivatives and partly into 9-amino compounds.

Reactions of t-Boc-Protected Amines with Difluorocarbene

Synthesis ◽  
2019 ◽  
Vol 51 (12) ◽  
pp. 2579-2583 ◽  
Author(s):  
Andrii Gerasov ◽  
Alexander Shivanyuk ◽  
Volodymyr Fetyukhin ◽  
Oleg Lukin
Keyword(s):  
Double Bond ◽  
Secondary Amines ◽  
Primary Amines ◽  
Primary And Secondary Amines

The reactions of t-Boc-protected secondary and primary amines with difluorocarbene generated from trimethylsilyl (fluorosulfonyl)difluoroacetate [Me3SiOC(O)CF2SO2F] (TFDA) in toluene at 110 °C results in the replacement of t-Bu by difluoromethyl in the t-Boc group. This reaction can be carried out in the presence of CH2Br and COOMe moieties in the structure of the protected amine. In the example of a t-Boc-protected amine containing a C=C double bond, replacement of the t-Bu group and/or cyclodifluoropropanation takes place. Difluoromethyl esters are shown to react with primary and secondary amines yielding the corresponding ureas.

TRIMETHYL ORTHOBORATE – AMINE INCLUSION COMPOUNDS

1962 ◽  
Vol 40 (9) ◽  
pp. 1805-1815
Author(s):  
D. M. Young ◽  
C. D. Anderson
Keyword(s):  
Vapor Pressure ◽  
Inclusion Compounds ◽  
Room Temperature ◽  
Secondary Amines ◽  
Crystalline Inclusion ◽  
X Ray Diffraction ◽  
Crystalline Inclusion Compounds ◽  
X Ray ◽  
New Class ◽  
Primary And Secondary Amines

A new class of non-stoichiometric crystalline inclusion compounds has been discovered, having the general formula[Formula: see text]where 0.5 < n < 1.0 and 0 < x < 3 depending on the method of preparation and on the nature of the amine and solvent. Such compounds have been prepared with ammonia and a variety of primary and secondary amines. Among the solvents which can be incorporated into the crystals are alcohols, ketones, ethers, esters, nitriles, nitroparaffins, and hydrocarbons. Such compounds are also formed by triphenyl orthoborate, with 1.7 < n < 2.4 and 1.2 < x < 1.6.The incorporated solvent has been shown to exert a definite vapor pressure. Furthermore, many of the compounds sublime at room temperature to form large transparent crystals which also contain incorporated solvent. The mechanism probably involves dissociation, followed by reassociation on the walls of the vessel. Preliminary X-ray diffraction measurements suggest that the trimethyl orthoborate – ammonia inclusion compounds have essentially the same crystal lattice as pure trimethyl orthoborate – ammonia.

Palladium Complexes of 2-Pyridin-2-yl Substituted 1,3-Bis(diphenylphosphino)propane:  Highly Active Catalysts for the Room-Temperature Copolymerization of Carbon Monoxide with Ethene

2002 ◽  
Vol 21 (20) ◽  
pp. 4147-4158 ◽  
Author(s):  
Simon Doherty ◽  
Edward G. Robins ◽  
Mark Nieuwenhuyzen ◽  
Paul A. Champkin ◽  
William Clegg
Keyword(s):  
Carbon Monoxide ◽  
Room Temperature ◽  
Palladium Complexes ◽  
Highly Active
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