- Palladium-Catalyzed Annulation of Arylbenzamides with Diaryliodonium Salts
-
By using diaryliodonium salts, a cylization has been accomplished in the synthesis of N-aryl phenanthridinone derivatives via a cascade of ortho-arylation and Csp2-N bond formation in the presence of palladium catalyst. The reaction exhibits a broad compatibility of readily available N-arylnaphthamides. (Figure presented.).
- Pan, Cheng,Wang, Limin,Han, Jianwei
-
supporting information
p. 268 - 273
(2021/11/09)
-
- The Pd-catalyzed synthesis of difluoroethyl and difluorovinyl compounds with a chlorodifluoroethyl iodonium salt (CDFI)
-
Herein, we report a simple and efficient method for the direct installation of chlorodifluoroethyl group onto aromatic molecules of various aromatic amides with a new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt (CDFI). Moreover, the chlorodifluoroeth
- Niu, Yaru,Cao, Chengyao Kimmy,Ge, Chenxin,Qu, Hongmei,Chen, Chao
-
supporting information
p. 1541 - 1544
(2021/10/01)
-
- Rhodium-Catalyzed Electrooxidative C?H Olefination of Benzamides
-
Metal-catalyzed chelation-assisted C?H olefinations have emerged as powerful tools for the construction of functionalized alkenes. Herein, we describe the rhoda-electrocatalyzed C?H activation/alkenylation of arenes. The olefinations of challenging electron-poor benzamides were thus accomplished in a fully dehydrogenative fashion under electrochemical conditions, avoiding stoichiometric chemical oxidants, and with H2 as the only byproduct. This versatile alkenylation reaction also features broad substrate scope and used electricity as a green oxidant.
- Ackermann, Lutz,Struwe, Julia,Zhang, Yan
-
p. 15076 - 15080
(2020/06/20)
-
- Tandem Transformation of Aldoximes to N-Methylated Amides Using Methanol
-
Tandem conversion of aldoximes to N-methylated amides with methanol in presence of a single Ru(II) catalyst is accomplished through the Ru(II)-mediated rearrangement followed by the reductive N-methylation. Employing this protocol, several aldoximes were directly transformed to the N-methylated amides using methanol. Kinetic experiments with H218O advocated that the aldoxime is acted as the nucleophile during the aldoxime to amide rearrangement process. Involvement of nitrile intermediate during this transformation is realized from the kinetic study. (Figure presented.).
- Paul, Bhaskar,Maji, Milan,Panja, Dibyajyoti,Kundu, Sabuj
-
supporting information
p. 5357 - 5362
(2019/11/14)
-
- Atom-Economical and Tandem Conversion of Nitriles to N-Methylated Amides Using Methanol and Water
-
A cobalt complex catalyzed tandem conversion of nitrile to N-methylated amide is described using a methanol and water mixture. Using this protocol, several nitriles were directly and efficiently converted to the desired N-methylated amides. Kinetic experiments using H2O18 and CD3OD suggested that water and methanol were the source of the oxygen atom and methyl group, respectively, in the final N-methylated amides. Importantly, the participation of active Co(I)-H species in this transformation was realized from the control experiment. The kinetic isotope effect (KIE) study suggested that the activation of the C-H bond of methanol was a kinetically important step. The Hammett plot confirmed that the reaction was faster with the electron deficient nitriles. In addition, the plausible pathway for the formation of N-methylated amides from the nitriles was supported by the computational study.
- Paul, Bhaskar,Maji, Milan,Kundu, Sabuj
-
p. 10469 - 10476
(2019/11/05)
-
- Rhenium-Catalyzed Phthalide Synthesis from Benzamides and Aldehydes via C-H Bond Activation
-
The [4 + 1] annulation of benzamides and aldehydes for phthalide synthesis was achieved via rhenium-catalyzed C-H activation, which demonstrates an unprecedented reaction pattern distinct from those of other transition-metal catalyses. The reaction also features readily available starting materials, a wide scope for both electro-rich and electro-deficient substrates, and the elimination of homoannulation byproducts.
- Jia, Bing,Yang, Yunhui,Jin, Xiqing,Mao, Guoliang,Wang, Congyang
-
p. 6259 - 6263
(2019/09/06)
-
- Ruthenium-Catalyzed Synthesis of N-Methylated Amides using Methanol
-
An efficient synthesis of N-methylated amides using methanol in the presence of a ruthenium(II) catalyst is realized. Notably, applying this process, tandem C-methylation and N-methylation were achieved to synthesize α-methyl N-methylated amides. In addition, several kinetic studies and control experiments with the plausible intermediates were performed to understand this novel protocol. Furthermore, detailed computational studies were carried out to understand the mechanism of this transformation.
- Paul, Bhaskar,Panja, Dibyajyoti,Kundu, Sabuj
-
supporting information
p. 5843 - 5847
(2019/08/26)
-
- I2-Catalyzed Oxidative Amidation of Benzylamines and Benzyl Cyanides under Mild Conditions
-
We report a novel and efficient method for the oxidation of benzylic carbons (amines and cyanides) into corresponding benzamides using a catalytic amount of I2 and TBHP as the green oxidant via the C-H bond cleavage of the benzylic carbon under mild reaction conditions. According to the literature survey, this is the first report for the oxidative amidation of benzylamines and decyanation of benzyl cyanides in one pot under metal-free conditions.
- Nageswara Rao, Sadu,Reddy, N. Naresh Kumar,Samanta, Supravat,Adimurthy, Subbarayappa
-
p. 13632 - 13642
(2017/12/26)
-
- Palladium-Catalyzed Direct C-H Trifluoroethylation of Aromatic Amides
-
A simple and direct C-H trifluoroethylation of aromatic amides has been developed. The protocol is applicable to a variety of aromatic amides, including ones derived from amino acids. The developed method can be used for further modifications of peptides. Preliminary mechanistic studies have been done by isolating the reaction intermediate.
- Maraswami, Manikantha,Pankajakshan, Sreekumar,Chen, Gang,Loh, Teck-Peng
-
supporting information
p. 4223 - 4226
(2017/08/23)
-
- Ru(II)-Catalyzed C-H Activation: Amide-Directed 1,4-Addition of the Ortho C-H Bond to Maleimides
-
Maleimide has been used as a selective coupling partner to generate conjugate addition products exclusively. The typical Heck-type oxidative coupling that occurs when alkenes are used is avoided by choosing maleimide as an alkene, which cannot undergo β-hydride elimination due to the unavailability of a syn-periplanar β-hydrogen atom. The amide nitrogen, which is notorious for undergoing tandem reactions to generate spirocyclic or annulation products under cross-coupling conditions, remains innocent in this report. Along with the substrate scope, a robustness screen has been performed to analyze the performance of amide as a directing group in the presence of other directing groups and also to examine the tolerance of the reaction conditions for other frequently encountered functional groups.
- Keshri, Puspam,Bettadapur, Kiran R.,Lanke, Veeranjaneyulu,Prabhu, Kandikere Ramaiah
-
p. 6056 - 6065
(2016/07/26)
-
- Transition-metal-free transformation of aryl bromides into aromatic esters and amides via aryl trichloromethyl ketones
-
A variety of aryl bromides have been treated with Mg and then chloral, followed by tBuOCl and subsequently alcohols or amines to produce the corresponding aromatic esters or amides in good yields via the formation of aryl trichloromethyl ketones as intermediates. These reactions are examples of a transition-metal-free one-pot preparation of aromatic esters and amides from aryl bromides. Aryl bromides have been treated with Mg and then chloral, followed by tBuOCl or tBuOCl with I2 as an additive, and subsequently alcohols or amines to form the corresponding aromatic esters and aromatic amides via aryl trichloromethyl ketones as intermediates. Copyright
- Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
-
p. 7815 - 7822
(2013/12/04)
-
- A novel neutral organic electron donor with record half-wave potential
-
Tricyclic donor 26 has been prepared and is the most reducing neutral ground-state organic molecule known, with an oxidation potential 260 mV more negative than the previous record. Cyclic voltammetry shows that a 2-electron reversible redox process occurs in DMF as solvent at -1.46 V vs. Ag/AgCl.
- Farwaha, Hardeep S.,Bucher, Goetz,Murphy, John A.
-
p. 8073 - 8081
(2013/12/04)
-
- Cross coupling of acyl and aminyl radicals: Direct synthesis of amides catalyzed by Bu4NI with TBHP as an oxidant
-
A radical solution: A Bu4NI/tert-butyl hydroperoxide (TBHP) catalyzed synthesis of amides through a cross-coupling reaction between acyl and aminyl radicals is described. This method involves the combination of aldehyde C-H bond functionalization and decarbonylation of N,N-disubstituted formamides (see scheme). The cross-coupling is metal-free, has a wide substrate scope, operational simplicity, and gives high yields on scale-up. Copyright
- Liu, Zhaojun,Zhang, Jie,Chen, Shulin,Shi, Erbo,Xu, Yuan,Wan, Xiaobing
-
supporting information; scheme or table
p. 3231 - 3235
(2012/05/05)
-
- Ruthenium-catalyzed oxidative annulation by cleavage of C-H/N-H bonds
-
Bond activation in action: Unprecedented ruthenium-catalyzed oxidative annulations of alkynes through cleavage of C-H bonds set the stage for an efficient 1(2H)-isoquinolone synthesis with ample scope (see scheme; tAm=tert-amyl). Mechanistic studies provided strong evidence for a rate-limiting C-H bond metalation through carboxylate assistance. Copyright
- Ackermann, Lutz,Lygin, Alexander V.,Hofmann, Nora
-
supporting information; experimental part
p. 6379 - 6382
(2011/09/12)
-
- The scope and limitation of nickel-catalyzed aminocarbonylation of aryl bromides from formamide derivatives
-
(Chemical Equation Presented) Nickel-catalyzed aminocarbonylation of aryl halides is described. A well-defined air-stable nickel-phosphite catalytic system (Ni(OAc)2 · 4H2O/phosphite 1) effectively promoted the aminocarbonylation of
- Jo, Youngshin,Ju, Jinhun,Choe, Jaehoon,Kwang, Ho Song,Lee, Sunwoo
-
supporting information; experimental part
p. 6358 - 6361
(2009/12/08)
-
- Metal-free reductive cleavage of N-O bonds in weinreb amides by an organic neutral super-electron donor
-
The scope of neutral organic super-electron donors as reducing agents has been extended to include the reductive cleavage of N-O bonds in Weinreb amides. This methodology proved to be applicable to a large array of substrates to afford their reduced counterparts in good to excellent yields. The variation in reactivity within the set of tested amides is rationalised. Georg Thieme Verlag Stuttgart.
- Cutulic, Sylvain P. Y.,Murphy, John A.,Farwaha, Hardeep,Zhou, Sheng-Ze,Chrystal, Ewan
-
experimental part
p. 2132 - 2136
(2009/04/08)
-
- PREPARATION AND UTILITY OF SUBSTITUTED ALLYLAMINES
-
Disclosed herein are substituted allylamines having structural Formula I, processes of preparation thereof, pharmaceutical compositions thereof, and the methods of their use thereof. (I)
- -
-
Page/Page column 64; 70
(2008/12/06)
-
- Room-temperature debenzylation of N-benzylcarboxamides by N-bromosuccinimide
-
A simple and highly efficient method has been developed with which to cleave the N-benzyl group on N-mono- or disubstituted carboxamides using N-bromosuccinimide (NBS) at room temperature. All the 31 substrates examined showed moderate to excellent deprotection yields. Our study also indicated that the debenzylation may involve an oxygen/light initiated free radical mechanism. Georg Thieme Verlag Stuttgart.
- Kuang, Liping,Zhou, Jing,Chen, Sheng,Ding, Ke
-
p. 3129 - 3134
(2008/03/28)
-
- Synthesis of 11C-labelled amides by palladium-mediated carboxamination using [11C]carbon monoxide, in situ activated amines and 1,2,2,6,6-pentamethylpiperidine
-
Twenty-seven 11C-labelled amides were synthesised using [11C]carbon monoxide in low concentrations, palladium(0), organohalides and amines in a small micro-autoclave (200 μL). The focus of the study was to improve the radiochemical yields in this palladium-mediated amide synthesis when employing less-reactive amines, such as methylamine, [(2R)-1-ethylpyrrolidin-2-yl]methylamine (40) and 2-(pyridin-2-yl)ethanamine (41). The radiochemical yields were improved when utilizing 1,2,2,6,6-pentamethylpiperidine (pempidine) in combination with the amine substrates. The 11C-labelled amides were obtained mostly in high radiochemical yields (in the range 16-94%) and the specific radioactivity varied between 650 and 1250GBq/μmol. 1-(1,3-Benzodioxol-5-yl[13C]carbonyl)piperidine (6a) was synthesised to verify the labelling position (δ = 169.8 ppm) using 13C NMR spectroscopy. The radiochemical purity of the target compounds was determined by analytical HPLC and exceeded 95%. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Karimi, Farhad,Langstroem, Bengt
-
p. 2132 - 2137
(2007/10/03)
-
- Intramolecular Diels-Alder Reactions. 4. Additions to Naphthalene
-
N-Methyl-N-2-propynyl-1-naphthalenecarboxamide, N-methyl-N-2-propynyl-1-naphthaleneacetamide, and N-methyl-N-3-butynyl-1-naphthalenecarboxamide undergo intramolecular Diels-Alder reactions at 190 deg C, 250 deg C, and 270 deg C to give lactams 1, 6, and 9, respectively.The cyclization temperatures are higher by 80-120 deg C as compared to those of the corresponding anthracene derivatives.Elaboration of lactam 6 gave the trans-4a-aryldecahydroisoquinoline derivative 7a which, as the (-) isomer, was shown to have the same absolute stereochemistry as morphine.
- Ciganek, Engelbert,Wuonola, Mark A.,Harlow, Richard L.
-
p. 1251 - 1258
(2007/10/02)
-