13807-57-3Relevant academic research and scientific papers
Alkynylation of aryl bromides with propargylamines catalyzed by a palladium-tetraphosphine complex
Lemhadri, Mhamed,Doucet, Henri,Santelli, Maurice
, p. 1359 - 1367 (2005)
The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for the alkynylation of aryl bromides with propargylamines. Higher reactions rates were observed with N,N- dialkylpropargylamines than with N-methylpropargylamine or propargy lamine. A wide variety of substituents such as alkyl, phenyl, methoxy, dimethylamino, fluoro, trifluoromethyl, acetyl, benzoyl, formyl, carboxylate, nitro, or nitrile, on the aryl bromides are tolerated. High turnover numbers can be obtained with most of these aryl bromides. The coupling reaction of sterically very congested aryl bromides such as 9-bromoanthracene or 2,4,6- triisopropylbromobenzene also proceeds in good yields. Georg Thieme Verlag Stuttgart.
Nano and Sub-nano Gold–Cobalt Particles as Effective Catalysts in the Synthesis of Propargylamines via AHA Coupling
Bensaad, Meriem,Berrichi, Amina,Bachir, Redouane,Bedrane, Sumeya
, p. 1068 - 1079 (2020/09/11)
Abstract: Titania supported Au–Co catalysts with nano- and sub-nanoparticles, were prepared with 1% Au and different contents of cobalt by one pot deposition precipitation with urea. Monometallic gold and cobalt catalysts were also prepared by the same me
Glyoxylic Acid: A Carboxyl Group-Assisted Metal-Free Decarboxylative Reaction Toward Propargylamines
Huang, Liliang,Xie, Yujuan,Ge, Panyuan,Huang, Junhai,Feng, Huangdi
supporting information, p. 2448 - 2451 (2021/06/28)
Readily available propargylamines are not only fundamental building blocks in organic synthesis, but also possess many prominent biological activities. A highly efficient, concise and environmentally benign decarboxylative reaction of glyoxylic acid monohydrate with secondary amines and alkynes has been elaborated, and a variety of propargylamines are delivered in moderate to good yields under metal-free conditions. A mechanism involving a carboxyl group that assists the reactivity of alkynes, which makes the procedure of Michael addition proceeded smoothly, has been proposed.
Oxidative C-C bond formation and C-N bond cleavage catalyzed by complexes of copper(i) with acridine based (E N E) pincers (E = S/Se), recyclable as a catalyst
Gupta, Sonu,Dubey, Pooja,Singh, Ajai K.,Jain, Nidhi
, p. 10129 - 10137 (2019/07/15)
Copper(i) complexes of 4,5-bis((phenylthio/seleno)methyl)acridine, [CuLBr] (C1 and C2) (L = L1/L2; pincer type (E N E) ligand), were synthesized and found to be thermally stable, and moisture and air insensitive. The complexes and ligands were characterized by multinuclei NMR and single crystal X-ray diffraction. In both complexes C1 and C2, ligands L1 and L2 coordinate with Cu in a pincer mode furnishing two six-membered chelate rings, with the distorted tetrahedral geometry of donor atoms around Cu. The Cu-S and Cu-Se bond lengths (?) are 2.2482(17)-2.2979(16) and 2.3603(14)-2.4177(13) respectively. These complexes served as efficient catalysts for cross dehydrogenative coupling of unactivated tertiary amines with unactivated terminal alkynes, and cleavage of the benzylic (C-N) bond of N,N dimethylbenzylamines under oxidative solvent-free conditions. The reactions were found to be highly selective, and no over-oxidation to acid was observed. A low catalytic loading of 1.0 mol% was good enough to bring about both these transformations with recyclability up to five times.
Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst
Dang-Bao, Trung,Pradel, Christian,Favier, Isabelle,Gómez, Montserrat
, p. 2832 - 2846 (2017/08/23)
Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly prepared from Cu(I) and Cu(II) precursors in glycerol and in the presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vapor pressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solid state, exhibiting relevantly homogeneous colloidal dispersions, also even after catalysis. CuNPs coming from the well-defined coordination complex di-μ-hydroxobis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride {[Cu(κ2-N,N-TMEDA)(μ-OH)]2Cl2} have been highly efficient in C–C and C–heteroatom bond formation processes. This new catalytic system has proved its performance in C–N couplings and in the synthesis of differently substituted propargylic amines through cross-dehydrogenative couplings, multi-component reactions such as A3 (aldehyde-alkyne-amine) and KA2 (ketone-alkyne-amine) couplings, as well as in the formation of heterocycles such as benzofurans, indolizines, and quinolines under smooth conditions. No significant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES) analyses, proving a highly efficient immobilization of copper nanoparticles in glycerol. From a mechanistic point of view, spectroscopic data (infrared and ultraviolet-visible spectra) agree with a surface-like catalytic reactivity. (Figure presented.).
Cu6Se4.5 Nanoparticles from a single source precursor: Recyclable and efficient catalyst for cross-dehydrogenative coupling of tertiary amines with terminal alkynes
Gupta, Sonu,Joshi, Hemant,Jain, Nidhi,Singh, Ajai K.
, p. 135 - 142 (2016/07/07)
The use of copper selenide nanocatalyst for an efficient and regioselective cross-dehydrogenative coupling (CDC) of tertiary amines with terminal alkynes in the presence of tert-butyl hydroperoxide as the oxidant is demonstrated for the first time. The ca
A highly efficient gold-catalyzed photoredox α-C(sp3)-H alkynylation of tertiary aliphatic amines with sunlight
Xie, Jin,Shi, Shuai,Zhang, Tuo,Mehrkens, Nina,Rudolph, Matthias,Hashmi, A. Stephen K.
supporting information, p. 6046 - 6050 (2015/05/13)
A new α-C(sp3)-H alkynylation of unactivated tertiary aliphatic amines with 1-iodoalkynes as radical alkynylating reagents in the presence of [Au2(μ-dppm)2]2+ in sunlight provides propargylic amines. Based on mechanistic studies, a C-C coupling of an α-aminoalkyl radical and an alkynyl radical is proposed for the C(sp3)-C(sp) bond formation. The mild, convenient, efficient, and highly selective C(sp3)-H alkynylation reaction shows excellent regioselectivity and good functional-group compatibility. A scale-up to gram quantities is possible with sunlight used as a clean and sustainable energy source.
Metal-free multicomponent coupling reaction of aliphatic amines, formaldehyde, organoboronic acids, and propiolic acids for the synthesis of diverse propargylamines
Wang, Jiayi,Shen, Qiaoying,Zhang, Jiayu,Song, Gonghua
supporting information, p. 903 - 906 (2015/02/05)
A metal-free multicomponent coupling reaction of aliphatic amines, formaldehyde, organoboronic acids, and propiolic acids has been reported for the synthesis of diverse propargylamines. This transformation involves a MCR2 of PBM and decarboxylative three-component coupling reactions.
Continuous flow reactions in water for the synthesis of propargylamines via a metal-free decarboxylative coupling reaction
Jung, Bongkyun,Park, Kyungho,Song, Kwang Ho,Lee, Sunwoo
, p. 4697 - 4700 (2015/07/28)
Abstract A range of propargylamines was synthesized via the metal-free decarboxylative coupling of alkynyl carboxylic acids with amines and paraformaldehyde in water, using a continuous flow reaction system. Aryl- and alkyl-substituted propiolic acids were found to react with secondary amines in the presence of paraformaldehyde, at 140°C in water to give the desired propargylamines in good yield.
Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite
Alonso, Francisco,Arroyo, Adrián,Martín-García, Iris,Moglie, Yanina
supporting information, p. 3549 - 3561 (2016/01/25)
A wide range of catalysts based on supported copper nanoparticles have been prepared and tested in the cross-dehydrogenative coupling of tertiary amines and terminal alkynes. Copper nanoparticles on zeolite Y were found to be the most effective catalyst in the presence of tert-butyl hydroperoxide as the oxidant. Contrary to the previously reported methodologies involving copper catalysts, reactions have been accomplished without the need of an inert atmosphere and in the absence of solvent, using 1.5mol% catalyst. A variety of tertiary amines, including aromatic, benzylic and aliphatic ones, have been coupled with both aromatic and aliphatic alkynes to furnish the corresponding propargylamines in moderate-to-excellent yields. The procedure has been successfully scaled-up to 12mmol with a high conversion (93%). Moreover, the catalyst has been reused in seven cycles maintaining a good performance. Its catalytic activity has been compared with that of an array of commercial copper catalysts, being superior as regards the conversion and minimizing the alkyne homocoupling as a side reaction. The negative filtration test points to a heterogeneous nature of the process. Based on compelling experimental evidence, a novel reaction mechanism has been delineated which outlines the essential role of free radicals and the couple copper(I)/copper(II).
