cas 3400-22-4, 4-METHOXY-N-METHYLBENZAMIDE

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HYDRATION OF N-MONOSUBSTITUTED AMIDES IN THE BINARY SOLVENTS DIOXANE-D2O AND DIOXANE-H2O
The molecular-level stucture of hydrated N-monosubstituted amides in aqueous media has been studied by measuring the infrared absorption spectra due to the C=O stretching (or amide I band) of a series of N-monosubstituted amides (RCONHR') in dioxan-D2O and dioxan-H2O mixtures.Three kinds of hydrated species of the secondary amides have been identified, namely monohydrated amide (II) (at the amide oxygen), dihydrated amide (III) (monohydrated at both the amide oxygen and the amide NH), and trihydrated amide (IV) (dihydrated at the amide oxygen and monohydrated at the amide NH).With increasing water content, the relative amounts of the hydrated amides increases in the order IIIIIIV.In pure heavy water, all of the amide molecules are hydrated, and two or three hydration states are in equilibrium.The degree of hydration is little influenced by the electronic character of the substituent R, whereas it is considerably influenced by the hydrophobic character of the substituent R'.As to the H/D isotope effect, the hydrogen bonding strength of C=O...HOH is stronger than that of C=O...DOD for N-alkylbenzamides.
Kobayashi, Mitsue,Nishioka, Kohji
p. 1247 - 1251
(1987)
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Assemblies of 1,4-Bis(diarylamino)naphthalenes and Aromatic Amphiphiles: Highly Reducing Photoredox Catalysis in Water
Host-guest assemblies of a designed 1,4-bis(diarylamino)naphthalene and V-shaped aromatic amphiphiles consisting of two pentamethylbenzene moieties bridged by an m -phenylene unit bearing two hydrophilic side chains emerged as highly reducing photoredox catalysis systems in water. An efficient demethoxylative hydrogen transfer of Weinreb amides has been developed. The present supramolecular strategy permits facile tuning of visible-light photoredox catalysis in water.
Abe, Manabu,Akita, Munetaka,Chitose, Youhei,Hyodo, Yuki,Koike, Takashi,Takahashi, Keigo,Yoshizawa, Michito
supporting information

(2021/10/21)

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
Cao, Chengyao Kimmy,Chen, Chao,Ge, Chenxin,Niu, Yaru,Qu, Hongmei
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(2021/10/01)

Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids, their oxyphilic reactivity and inertness to amines
Thiophosphinoylation of N-methyl p-substituted benzohydroxamic acids using disulfanes (method A) or diphenylphosphinothioyl chloride (method B) provides only one conformer of the respective O-phosphothioyl derivative (X-ray and NMR analysis). Undergoing t
Majewski, Arkadiusz,Chojnacki, Jaros?aw,Przychodzeń, Witold
p. 1077 - 1091
(2021/01/11)

Method for synthesizing amide by using methyl arene and amine in water phase
The invention provides a high-efficient method of synthesizing amide with methyl aromatics and amine. In the method, with the methyl aromatics and the amine as the raw materials in the water phase and TBHP and TBAI respectively as an oxidizing agent and a catalyst, a sp3 C-H bond and a sp3 N-H bond are broken and a C-N bond is formed. Compared with a conventional method of synthesizing the amide from oxidized amide, in which an activated acyl group or amine is required, the method is carried out with water as the solvent so that the method is not only economical but also environmental-protective. The method has a very good application prospect in the field of synthesizing polypeptide, protein and drugs in future.
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(2021/03/06)

Catalytic asymmetric [3+2] cycloaddition of isomünchnones with methyleneindolinones
An efficient enantioselective [3+2] cycloaddition of isomünchnones with methyleneindolinones that are generated by anin situintramolecular addition of the carbonyl group to rhodium carbenes is realized with a chiralN,N′-dioxide/Zn(ii) complex as a Lewis acid. A series of chiral oxa-bridged 3-spiropiperidines are obtained in high yields with excellent dr and excellent ee values.
Feng, Xiaoming,Hu, Xinyue,Lin, Lili,Wang, Kaixuan,Xu, Chaoran,Zhou, Yuqiao
supporting information
p. 8917 - 8920
(2021/09/10)

Copper-Catalyzed Radical N-Demethylation of Amides Using N-Fluorobenzenesulfonimide as an Oxidant
An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.
Yi, Xuewen,Yi, Xuewen,Lei, Siyu,Liu, Wangsheng,Che, Fengrui,Yu, Chunzheng,Liu, Xuesong,Wang, Zonghua,Zhou, Xin,Zhang, Yuexia
supporting information
p. 4583 - 4587
(2020/05/05)

Dealkoxylation ofN-alkoxyamides without an external reductant driven by Pd/Al cooperative catalysis
Lewis acid-assisted palladium-catalysed dealkoxylation ofN-alkoxyamides has been developed. This reaction proceeded smoothly with a range ofN-alkoxyamides in the absence of an external reductant, thereby establishing a convenient and reductant-free protocol. In addition, a gram-scale reaction could be achieved. Preliminary mechanistic investigations indicated that β-hydrogen elimination from a palladium alkoxide intermediate generated an intramolecular hydride source.
Suzuki, Hirotsugu,Shiomi, Takahiro,Yoneoka, Kenji,Matsuda, Takanori
supporting information
p. 7545 - 7548
(2020/10/15)

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)

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)

Hydrogen Bond Directed ortho-Selective C?H Borylation of Secondary Aromatic Amides
Reported is an iridium catalyst for ortho-selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen-bond interactions. The BAIPy-Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho-C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
Bai, Shao-Tao,Bheeter, Charles B.,Reek, Joost N. H.
supporting information
p. 13039 - 13043
(2019/07/31)

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
supporting information
p. 6259 - 6263
(2019/09/06)

Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
p. 11823 - 11838
(2019/10/02)

Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines
Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N -methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.
Gim, Hyo Jin,Jung, Michael E.
supporting information
p. 2548 - 2552
(2019/06/08)

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)

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)

Aerobic Activation of C-H Bond in Amines Over a Nanorod Manganese Oxide Catalyst
The development of heterogeneous catalysts for the synthesis of pharmaceutically relevant compounds is always important for chemistry research. Here, we report a selective aerobic oxidation of aromatic and aliphatic amines to corresponding amides over a nanorod manganese oxide (NR-MnOx) catalyst. The kinetic studies reveal that the NR-MnOx catalyzed amine-to-amide reaction proceeds the oxidative dehydrogenation of the amines into nitriles, followed by hydrolysis of nitrile into amides. The NR?MnOx exhibits fast kinetics and high selectivities in these steps, as well as hinders the by-product formation. More importantly, the NR-MnOx catalyst is stable and reusable in the continuous recycle tests with water as a sole by-product, exhibiting superior sustainability and significant advancement to outperform the traditional amide production route in acidic or basic media with toxic by-products.
Wang, Hai,Wang, Liang,Wang, Sai,Dong, Xue,Zhang, Jian,Xiao, Feng-Shou
p. 401 - 406
(2018/08/11)

Nickel-catalyzed aminocarbonylation of aryl halides with carbamoylsilanes: efficient synthesis of secondary (primary) aromatic amides
A nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source leading to corresponding secondary or primary aromatic amides has been developed, in which the methoxymethyl and benzyl were used as amino protecting group. The protocol tolerates a broad range of aryl halides bearing different functional groups to afford good yields of aryl amides under mild reaction conditions. The types and the relative positions of substituents on the aryl ring make a notable impact on the coupling efficiency. The plausible mechanism of nickel-catalyzed aminocarbonylation has been suggested.
Chen, Jianxin,Chen, Wenwen,Wen, Xueping
(2019/08/30)

Selective N-Monoalkylation of Amide Derivatives with Trialkyl Phosphates
A highly selective and easily handled monoalkylation of primary amide derivatives by using trialkyl phosphates as alkylating reagents in cyclopentyl methyl ether (CPME) was developed. Various monoalkylated amide derivatives were efficiently synthesized by changing the alkyl moiety (e.g., methyl, ethyl, butyl, or benzyl) of the trialkyl phosphate. These phosphate reagents are relatively stable and easily available, and CPME is a useful solvent in process chemistry.
Asai, Shota,Ban, Kazuho,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
supporting information
p. 322 - 325
(2017/10/31)

Metal-Free Thermal Activation of Molecular Oxygen Enabled Direct α-CH2-Oxygenation of Free Amines
Direct oxidation of α-CH2 group of free amines is hard to achieve due to the higher reactivity of amine moiety. Therefore, oxidation of amines involves the use of sophisticated metallic reagents/catalyst in the presence or absence of hazardous oxidants under sensitive reaction conditions. A novel method for direct C-H oxygenation of aliphatic amines through a metal-free activation of molecular oxygen has been developed. Both activated and unactivated free amines were oxygenated efficiently to provide a wide variety of amides (primary, secondary) and lactams under operationally simple conditions without the aid of metallic reagents and toxic oxidants. The method has been applied to the synthesis of highly functionalized amide-containing medicinal drugs, such as O-Me-alibendol and -buclosamide.
Ghosh, Santanu,Jana, Chandan K.
p. 260 - 266
(2018/02/19)

Mechanistic Study of SmI2/H2O and SmI2/Amine/H2O-Promoted Chemoselective Reduction of Aromatic Amides (Primary, Secondary, Tertiary) to Alcohols via Aminoketyl Radicals
Samarium(II) iodide-water and samarium(II) iodide-water-amine complexes have been recognized as valuable reagents for the selective generation of aminoketyl radicals from amides and derivatives. The resulting aminoketyl radicals can undergo reduction or reductive cyclization pathways, providing a powerful method for (i) direct synthesis of alcohols from amides by the challenging N-C bond scission and (ii) synthesis of nitrogen-containing heterocycles via polarity reversal of the amide bond. This report describes mechanistic investigation into samarium(II) iodide-water and samarium(II) iodide-water-amine-mediated generation of benzylic aminoketyl radicals from aromatic primary, secondary, and tertiary amides (benzamides). The mechanistic experiments suggest that the rate and selectivity of the reduction is closely dependent on the water concentration and the type of amide undergoing the reduction. The data also suggest that benzylic aminoketyl radicals generated in the reduction of benzamides are significantly more dependent on the electronic effects of α-substitution than the corresponding aminoketyl radicals generated by single-electron transfer to unactivated aliphatic amides; however, little variation in terms of steric influence of N-substituents is observed. These observations will have implications for the design of reductive processes involving Sm(II)-mediated reduction of amides and reductive umpolung cyclizations via aminoketyl radicals as a key step.
Huq, Syed R.,Shi, Shicheng,Diao, Ray,Szostak, Michal
p. 6528 - 6540
(2017/07/15)

Visible-Light-Promoted C-H Arylation by Merging Palladium Catalysis with Organic Photoredox Catalysis
The use of a dual palladium/organic photoredox catalytic system enables the directed arylation of arenes with aryldiazonium salts with a broad substrate scope at room temperature under mild reaction conditions. This study thus serves as not only an alternative route for the biaryl motifs but also a new example for the application of an organic photoredox catalyst.
Jiang, Jian,Zhang, Wen-Man,Dai, Jian-Jun,Xu, Jun,Xu, Hua-Jian
p. 3622 - 3630
(2017/04/11)

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)

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)

Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source
Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.
Tong, Wenting,Cao, Pei,Liu, Yanhong,Chen, Jianxin
p. 11603 - 11608
(2017/11/10)

Nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source
The nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source is developed. The procedure can prepare both tertiary and secondary amides, and is applicable to various carbamoylsilanes and aryl halides containing differen
Wen, Xue-Ping,Han, Yu-Ling,Chen, Jian-Xin
p. 45107 - 45112
(2017/10/13)

Laser flash photolysis of nanocrystalline α-azido-: P -methoxy-acetophenone
Irradiation of nanocrystals of azide 1 results in a solid-to-solid reaction that forms imine 2 in high chemical yield. In contrast, solution photolysis of azide 1 yields a mixture of products, with 7 as the major one. Laser flash photolysis (LFP) of a nanocrystalline suspension of azide 1 in water shows selective formation of benzoyl radical 4 (λmax ～ 400 nm), which is short-lived (τ = 833 ns) as it intersystem crosses to form imine 2. In comparison, LFP of azide 1 in methanol reveals the formation of triplet alkylnitrene 10 (λmax ～ 340 nm). The selectivity observed in the solid-state is related to stabilization of the triplet ketone with (n,π?) configuration by the crystal lattice, which results in α-cleavage being favored over triplet energy transfer to the azido chromophore. Both the solid-state and solution reaction mechanisms are further supported by density functional theory calculations. Thus, laser flash photolysis has been used to effectively elucidate the medium dependent reaction mechanisms of azide 1.
Sarkar, Sujan K.,Gatlin, Devonna M.,Das, Anushree,Loftin, Breyinn,Krause, Jeanette A.,Abe, Manabu,Gudmundsdottir, Anna D.
p. 7380 - 7386
(2017/09/25)

Palladium-Catalyzed Oxidative Carbonylation of Aryl Hydrazines with CO and O2 at Atmospheric Pressure
Palladium-catalyzed aerobic oxidative aminocarbonylation and alkoxycarbonylation reactions with aryl hydrazines as coupling partners have been developed. The oxidative carbonylation of aryl hydrazines proceeded smoothly at atmospheric pressure CO, employi
Tu, Yongliang,Yuan, Lin,Wang, Tao,Wang, Changliu,Ke, Jiamei,Zhao, Junfeng
p. 4970 - 4976
(2017/05/12)

Aerobic thiyl radical addition/cyclization of N-methacryloyl benzamides for the synthesis of isoquinoline-1,3(2H,4H)-dione derivatives
A highly effective oxidative thiyl radical addition/cyclization of N-methacryloylbenzamides was explored using dioxygen as the sole terminal oxidant without the use of precious and/or toxic transition-metal catalysts. This method provides convenient access to a variety of useful sulfide-containing 4,4-disubstituted isoquinoline-1,3-diones by constructing C-S and C-C bonds in one step.
Yuan, Yan-Qin,Kumar, Pailla Santhosh,Zhang, Chun-Niu,Yang, Ming-Hua,Guo, Sheng-Rong
supporting information
p. 7330 - 7338
(2017/09/25)

Aminofluorene-Mediated Biomimetic Domino Amination-Oxygenation of Aldehydes to Amides
A conceptually novel biomimetic strategy based on a domino amination-oxygenation reaction was developed for direct amidation of aldehydes under metal-free conditions employing molecular oxygen as the oxidant. 9-Aminofluorene derivatives acted as pyridoxamine-5′-phosphate equivalents for efficient, chemoselective, and operationally simple amine-transfer oxygenation reaction. Unprecedented RNH transfer involving secondary amine to produce secondary amides was achieved. In the presence of 18O2, 18O-amide was formed with excellent (95%) isotopic purity.
Ghosh, Santanu,Jana, Chandan K.
supporting information
p. 5788 - 5791
(2016/11/29)

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)

Reductive N-O cleavage of Weinreb amides by sodium in alumina and silica gels: synthetic and mechanistic studies
The use of sodium in alumina and silica gels for the reductive cleavage of the N-O bond of N-methoxy-N-methylamides, commonly referred to as Weinreb amides, has been investigated. This method reduces a diverse set of Weinreb amides with different function
Jackson, James E.,O'Brien, Brittany N.,Kedzior, Sonya K.,Fryz, Gage R.,Jalloh, Fatmata S.,Banisafar, Arash,Caldwell, Michael A.,Braun, Max B.,Dunyak, Bryan M.,Dye, James L.
supporting information
p. 6227 - 6230
(2015/10/20)

Cobalt(III)-Catalyzed Directed C-H Allylation
The cobalt(III)-catalyzed allylation was developed for amide-directed C-H activation of arenes, heteroarenes, and olefins. A variety of allyl sources can be employed to introduce this useful functional group.
Gensch, Tobias,Vásquez-Céspedes, Suhelen,Yu, Da-Gang,Glorius, Frank
supporting information
p. 3714 - 3717
(2015/08/18)

One-Pot Direct Synthesis of Weinreb Amides from Aryl and Hetero Aryl Halides Using Co 2(CO) 8 as an Effective CO Source under Conventional Thermal Heating
A successful protocol for the synthesis of Weinreb amides directly from aryl halides via aminocarbonylation with N,O-dimethyl hydroxylamine using Co2(CO)8 as an in situ CO source has been demonstrated. The effects of various reaction parameters such as temperature, base, and CO source have also been investigated and optimized. GRAPHICAL ABSTRACT.
Baburajan, Poongavanam,Elango, Kuppanagounder P.
p. 541 - 548
(2015/10/29)

Iron-Catalyzed Acylative Dealkylation of N-Alkylsulfoximines
As a result of our recent investigations into the N-functionalization of sulfoximines, an iron-catalyzed dealkylative acylation of N-alkylsulfoximines has been developed. This process involves a Polonovski-type dealkylation of an N-alkylated sulfoximine to afford a reactive intermediate that is trapped in the presence of a suitable aldehyde or anhydride to afford N-acyl- and N-aroylsulfoximine derivatives in one pot. Subsequent cleavage of the acyl or aroyl group under acidic conditions generates a synthetically valuable NH-sulfoximine. The dealkylation of N-alkylsulfoximines has been developed utilizing TBHP as oxidant and a catalytic amount of iron chloride to furnish a range of N-acyl- and N-aroylsulfoximines. This method facilitates the use of N-alkyl protecting groups that provide very stable N-protected sulfoximine derivatives that can be readily modified at sites other than the nitrogen atom.
Lamers, Philip,Priebbenow, Daniel L.,Bolm, Carsten
p. 5594 - 5602
(2015/09/01)

Direct oxidative amidation between methylarenes and amines in water
An environmentally friendly direct oxidative amidation between methylarenes and free amines was developed. The aromatic amide could be prepared efficiently from raw chemicals by employing TBHP as a "green" oxidant with co-catalysis of TBAI and FeCl3 in water.
Wang, Tao,Yuan, Lin,Zhao, Zhenguang,Shao, Ailong,Gao, Meng,Huang, Yangfei,Xiong, Fei,Zhang, Huali,Zhao, Junfeng
supporting information
p. 2741 - 2744
(2015/05/27)

Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2°amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
Baburajan, Poongavanam,Elango, Kuppanagounder P.
supporting information
p. 1006 - 1010
(2015/02/19)

Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1 and cyclic and acyclic 2 amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
Baburajan, Poongavanam,Elango, Kuppanagounder P.
supporting information
p. 1006 - 1010
(2014/02/14)

Oxidative synthesis of benzamides from toluenes and DMF
An interesting oxidative procedure for the synthesis of benzamides has been developed through the cleavage of sp3CH bond of methyl arenes with N-substituted formamides. Various benzamides were prepared in low to moderate yields. Even though the
Feng, Jian-Bo,Wei, Duo,Gong, Jin-Long,Qi, Xinxin,Wu, Xiao-Feng
supporting information
p. 5082 - 5084
(2015/01/08)

Transition metal-free one-pot synthesis of 2-substituted 3-carboxy-4-quinolone and chromone derivatives
A novel one-pot synthesis of the 2-substituted 3-carboxy-4-quinolone/ chromone derivatives from readily available 3-oxo-3-arylpropanoates and amides/acyl chlorides is reported, without any transition metal aid. The Royal Society of Chemistry 2013.
Lin, Jian-Ping,Long, Ya-Qiu
supporting information
p. 5313 - 5315
(2013/06/27)

Re/Mg bimetallic tandem catalysis for [4+2] annulation of benzamides and alkynes via C-H/N-H functionalization
A rhenium-magnesium cocatalyzed [4+2] annulation of benzamides and alkynes via C-H/N-H functionalization is described. The reaction features a divergent and high level of diastereoselectivities, which are readily switchable by subtle tuning of reaction conditions. Thus, a wide range of both cis- and trans-3,4-dihydroisoquinolinones is expediently synthesized in a highly atom-economical manner. Moreover, mechanistic studies unraveled a tandem mode of action between rhenium and magnesium in the catalytic cycles.
Tang, Qiuzheng,Xia, Dexin,Jin, Xiqing,Zhang, Qing,Sun, Xiao-Qiang,Wang, Congyang
supporting information
p. 4628 - 4631
(2013/05/21)

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)

Copper-catalyzed N-methylation of amides and O-methylation of carboxylic acids by using peroxides as the methylating reagents
The copper-catalyzed N-methylation of amides and O-methylation of carboxylic acids by using peroxides as the methylating reagent are described. Various amides and carboxylic acids were methylated affording N-substituted amides and esters. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
Xia, Qinqin,Liu, Xiaolong,Zhang, Yuejiao,Chen, Chao,Chen, Wanzhi
supporting information
p. 3326 - 3329
(2013/07/26)

Peptide fragment coupling using a continuous-flow photochemical rearrangement of nitrones
Go with the flow: A general approach for amide bond formation by way of a continuous-flow photochemical rearrangement of nitrones was described (see scheme). Simple aryl-alkyl amide bonds as well as complex peptide bonds were constructed efficiently with a residence time less than 20minutes. A tetrapeptide was synthesized in this way and the method could be applied to peptide fragment coupling. Copyright
Zhang, Yuan,Blackman, Melissa L.,Leduc, Andrew B.,Jamison, Timothy F.
supporting information
p. 4251 - 4255
(2013/05/08)

Metal-free aryltrifluoromethylation of activated alkenes
Metal-free: The first metal-free aryltrifluoromethylation of activated alkenes has been developed. With this method, trifluoromethylated isoquinolinediones, spirobicycles, oxindoles, and α-aryl-β- trifluoromethylamides were obtained with high control of the regioselectivity. Copyright
Kong, Wangqing,Casimiro, Maria,Fuentes, Noelia,Merino, Estibaliz,Nevado, Cristina
p. 13086 - 13090
(2014/01/06)

Synthesis of N-alkyl and N-aryl isoquinolones and derivatives via Pd-catalysed C-H activation and cyclization reactions
Relatively less expensive Pd-catalysed oxidative coupling reactions for the preparation of N-alkyl and N-aryl substituted isoquinolones and their derivatives have been developed. A broad reaction scope has been demonstrated. In addition, studies of the reaction additives and mechanistic insights, as well as KIE studies for a better understanding of the reaction pathway, have been discussed.
Zhang, Nana,Li, Binyao,Zhong, Hongban,Huang, Jianhui
p. 9429 - 9439
(2013/01/15)

Rhodium(iii)-catalyzed oxidative carbonylation of benzamides with carbon monoxide
An efficient strategy for the oxidative carbonylation of aromatic amides via C-H/N-H activation to form phthalimides using an Rh(iii) catalyst has been developed. The reaction shows a preference for C-H bonds of electron-rich aromatic amides and tolerates a variety of functional groups. The Royal Society of Chemistry 2011.
Du, Ya,Hyster, Todd K.,Rovis, Tomislav
p. 12074 - 12076
(2011/12/14)

Microwave-assisted synthesis of weinreb and MAP aryl amides via pd-catalyzed heck aminocarbonylation using Mo(CO)6 or W(CO) 6
A simple and expedient process for the Heck aminocarbonylative synthesis of Weinreb and MAP amide acylating agents, from aryl halides, is reported. This methodology utilizes solid sources of CO making it readily accessible to chemists working in small-scale laboratory applications.
Wieckowska, Anna,Fransson, Rebecca,Odell, Luke R.,Larhed, Mats
supporting information; experimental part
p. 978 - 981
(2011/03/22)

Rhodium-catalyzed oxidative cycloaddition of benzamides and alkynes via C-H/N-H activation
The oxidative cycloaddition of benzamides and alkynes has been developed. The reaction utilizes Rh(III) catalysts in the presence of Cu(II) oxidants, and is proposed to proceed by N-H metalation of the amide followed by ortho C-H activation. The resultant rhodacycle undergoes alkyne insertion to form isoquinolones in good yield. The reaction is tolerant of extensive substitution on the amide, alkyne, and arene, including halides, silyl ethers, and unprotected aldehydes as substituents. Unsymmetrical alkynes proceed with excellent regioselectivity, and heteroaryl carboxamides are tolerated leading to intriguing scaffolds for medicinal chemistry. A series of competition experiments shed further light on the mechanism of the transformation and reasons for selectivity.
Hyster, Todd K.,Rovis, Tomislav
supporting information; experimental part
p. 10565 - 10569
(2010/09/17)

A facile synthesis of 2,3-disubstituted furo[2,3-b]pyridines
In a three-step sequence starting from readily available starting materials, 2,3-carbon disubstituted furo[2,3-b]pyridines can be accessed in good yields and purity. Furo[2,3-b]pyridines bearing ester, amide and ketone groups at the 2-position can be prepared with a variety of aryl and alkyl groups at the 3-position.
Beutner, Gregory L.,Kuethe, Jeffrey T.,Yasuda, Nobuyoshi
supporting information; experimental part
p. 781 - 784
(2009/05/11)

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)