- Pd-Catalyzed Oxidative Aminocarbonylation of Arylboronic Acids with Unreactive Tertiary Amines via C-N Bond Activation
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An efficient synthesis of tertiary amides from aryl boronic acids and inert tertiary amines through the oxidative carbonylation via C(sp3)-N bond activation is presented. This protocol significantly restricts the homocoupling biarylketone product. It involves the use of a homogeneous PdCl2/CuI catalyst and a heterogeneous Pd/C based catalyst, which promotes C(sp3)-N bond activation of tertiary amines with aryl boronic acids. This process represents a ligand-free, base-free, and recyclable catalyst along with an ideal oxidant like molecular oxygen.
- Kolekar, Yuvraj A.,Bhanage, Bhalchandra M.
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p. 14028 - 14035
(2021/05/29)
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- Supramolecular Pd(II) complex of DPPF and dithiolate: An efficient catalyst for amino and phenoxycarbonylation using Co2(CO)8 as sustainable C1 source
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Highly active, efficient and robust “dppf ligated tetranuclear palladium dithiolate complex” was synthesized and applied as a catalyst for chemical fixation of carbon monoxide for the synthesis value added chemicals such as tertiary amide and aromatic esters. The synthesized catalyst was characterized using different analytical techniques such as elemental analysis, 1H and 31P NMR spectroscopy. The use of Co2(CO)8 as a cheap, less toxic and low melting solid surrogate are additional advantages over the current protocol. The catalyst showed superior activity towards the Amino (10?3 mol % catalyst) and Phenoxycarbonylation (10-2 mol % catalyst) and high TON (104 to 103) and TOF (103 to 102 h-1). The Betol and Lintrin (active drug molecules) were synthesized under an optimized reaction condition. The scalability of the current protocol has been demonstrated up-to the gram level.
- Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Patel, Divya,Bhanage, Bhalchandra M.
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- HMF and furfural: Promising platform molecules in rhodium-catalyzed carbonylation reactions for the synthesis of furfuryl esters and tertiary amides
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A biomass involved rhodium-catalyzed carbonylative synthesis of furfuryl esters and tertiary amides has been developed. 5-Hydroxymethylfurfural (HMF) was used as both substrate and CO surrogate for the first time in a carbonylation reaction, and both alkyl and aryl iodides were tolerated well to afford the desired furfuryl esters in moderate to good yields. In addition, furfural was also utilized as a CO source for the synthesis of tertiary amides. A variety of tertiary amides were obtained in moderate to excellent yields with good functional groups compatibility. Notably, tertiary amines were used as the amine source through a C[sbnd]N bond cleavage pathway in the absence of additional oxidant.
- Qi, Xinxin,Zhou, Rong,Ai, Han-Jun,Wu, Xiao-Feng
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p. 215 - 221
(2019/11/25)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Pd/C-catalyzed aminocarbonylation of aryl iodides via oxidative C-N bond activation of tertiary amines to tertiary amides
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This work reports oxidative N-dealkylation/carbonylation of tertiary amines to tertiary amides by using molecular oxygen as a sole oxidant using a Pd/C catalyst. This protocol is free from ligands, additives, bases, and cocatalysts. Different tertiary amines as well as aryl iodides have been examined for this transformation, providing desired products in good to excellent yield.
- Mane, Rajendra S.,Bhanage, Bhalchandra M.
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p. 1223 - 1228
(2016/02/18)
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- Pd(ii)-catalyzed decarboxylative cross-coupling of oxamic acids with potassium phenyltrifluoroborates under mild conditions
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A novel Pd-catalyzed decarboxylative cross-coupling of oxamic acids with potassium phenyltrifluoroborates has been realized under mild reaction conditions. This method provides an efficient access to N-mono- or N,N-disubstituted benzamides and benzoates.
- Li, Mingzong,Wang, Cong,Fang, Ping,Ge, Haibo
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supporting information; experimental part
p. 6587 - 6589
(2011/06/25)
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- A practical synthesis of m-prostaglandin E synthase-1 inhibitor MK-7285
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(Chemical Equation Presented) A practical, kilogram-scale chromatography-free synthesis of mPGE synthase I inhibitor MK-7285 is described. The route features a convergent assembly of the core phenanthrene unit via amide-directed ortho-metalation and proxi
- Gosselin, Francis,Lau, Stephen,Nadeau, Christian,Trinh, Thao,O'Shea, Paul D.,Davies, Ian W.
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supporting information; experimental part
p. 7790 - 7797
(2010/03/05)
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- Ketopyrroles useful as ligands in organic iridium compositions
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The present invention provides novel ketopyrroles having structure XXIV wherein R2 is independently at each occurrence a deuterium atom, a halogen, a nitro group, an amino group, a C3-C40 aromatic radical, a C1-C50 aliphatic radical, or a C3-C40 cyclcoaliphatic radical; “a” is an integer from 0 to 3; and X1 and X2 are independently at each occurrence a bromine atom, a hydroxy group, or the group OR10, and wherein the group R10 is independently at each occurrence a deuterium atom, a halogen, a nitro group, an amino group, a C3-C40 aromatic radical, a C1-C50 aliphatic radical, or a C3-C40 cyclcoaliphatic radical. Ketopyrroles XXIV are useful ligands for the preparation of Type (1) and Type (2) organic iridium compositions. In one aspect, the present invention provides deuterated analogs of XXIV. Organic iridium compositions are useful in the preparation optoelectronic devices, such as OLED devices and photovoltaic devices exhibiting enhanced performance characteristics.
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Page/Page column 36
(2008/06/13)
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- p-Fluorobenzoyl Chloride for Characterization of Active Hydrogen Functional Groups by Fluorine-19 Nuclear Magnetic Resonance Spectrometry
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The base-catalyzed reactions of p-fluorobenzoyl chloride provide a convenient method for (19)F NMR analysis of alcohols, phenols, carboxylic acids, amines, and thiols.The (19)F chemical shift and yield data for p-fluorobenzoyl derivatives for nearly 100 compounds are presented.The yield data for these p-fluorobenzoyl derivatives suggest a simple, and in many cases, quantitative method for introducing a fluorine tagging group.The (19)F chemical shifts indicate a wide chemical shift range (ca. 10 ppm) for a large number of compounds.Furthermore, most chemical classes (e.g., phenols, alcohols, etc.) have fairly well resolved chemical shift regions.
- Spratt, M. P.,Dorn, H. C.
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p. 2038 - 2043
(2007/10/02)
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- INVESTIGATIONS ON N,N-DIALKYLBENZAMIDES BY NMR SPECTROSKOPY. PART II. A COMPARISON OF BARRIERS TO ROTATION ABOUT THE AMIDE C-N BOND IN PARA SUBSTITUTED N,N-DIMETHYL- AND N,N-DIETHYLBENZAMIDES
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The barriers to rotation about the amide C-N bond in a series of para-substituted N,N-dimethyl- and N,N-diethylbenzamides have been compared.A method allowing the detection using standard measurement conditions of small differences between barriers to rotation has been proposed.It has been stated that the barriers to rotation in N,N-dimethylbenzamides are ca. 2 kJ/mole higher than those in the corresponding N,N-diethylbenzamides and that the differences ΔMe-Et are at least partially due to those in entropies of activation.It has been observed that ΔMe-Et increases with the increasing electron donating properties of the para substituent .The observed phenomena have been rationalized in terms of steric interactions in the ground state of rotation in the molecules under investigation.
- Gryf-Keller, Adam,Terpinski, Jacek,Zajaczkowska-Terpinska, Ewa
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p. 1465 - 1471
(2007/10/02)
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