- Ni-Catalyzed Direct Carboxylation of Aryl C?H Bonds in Benzamides with CO2
-
The direct carboxylation of inert aryl C?H bond catalyzed by abundant and cheap nickel is still facing challenge. Herein, we report the Ni-catalyzed direct carboxylation of aryl C?H bonds in benzamides under 1 atm of CO2 to afford various methyl carboxylates or phthalimides, dealing with different post-processing. The reaction displays excellent functional group tolerance and affords moderate to high carboxylation yields under mild conditions. Detail mechanistic studies suggest that a Ni(0)?Ni(II)?Ni(I) catalytic cycle may be involved in this reaction. (Figure presented.).
- Pei, Chunzhe,Zong, Jiarui,Li, Bin,Wang, Baiquan
-
p. 493 - 499
(2021/12/08)
-
- Synthesis of N-unsubstituted cyclic imides from anhydride with urea in deep eutectic solvent (DES) choline chloride/urea
-
N-Unsubstituted cyclic imides were readily synthesized in deep eutectic solvent (DES) choline chloride (ChCl)/urea from anhydrides with urea. Urea serves as both a DES component and a nitrogen source, which endows the protocol with advantages of smooth reaction, easy separation of products, simple recovery and recycling of ChCl/urea.
- Liu, Luxiao,Zhang, Hong-Yu,Yin, Guohui,Zhang, Yuecheng,Zhao, Jiquan
-
p. 1351 - 1357
(2019/11/19)
-
- Intramolecular Reductive Cyclization of o-Nitroarenes via Biradical Recombination
-
A visible-light-induced/thiourea-mediated intramolecular cyclization of o-nitroarenes under mild conditions is realized for the first time, which provides an efficient and environmentally friendly way to access pharmaceutical relevant quinazolinone derivatives. The reaction can be easily extended to gram level by using a continuous-flow setup with high efficiency. Mechanistic investigation including control experiments, transient fluorescence, UV-vis spectra, and DFT calculations suggests that the formation of active biradical intermediates via intramolecular single electron transfer (SET) is key stage in the catalytic cycle.
- Lu, Cong,Su, Zhishan,Jing, Dong,Jin, Songyang,Xie, Lijuan,Li, Liangrui,Zheng, Ke
-
supporting information
p. 1438 - 1443
(2019/03/07)
-
- Metal-Free Synthesis of Polycyclic Quinazolinones Enabled by a (NH4)2S2O8-Promoted Intramolecular Oxidative Cyclization
-
An efficient metal-free, (NH4)2S2O8 mediated intramolecular oxidative cyclization for the construction of polycyclic heterocycles was disclosed. A series of polycyclic quinazolinone derivatives with good functional group tolerance were obtained in high yields. The natural products tryptanthrin and rutaecarpine, as well as their derivatives, were easily synthesized by this strategy. A preliminary mechanism study suggested the carbon-centered radical was involved in the catalytic cycle.
- Xie, Lijuan,Lu, Cong,Jing, Dong,Ou, Xinrui,Zheng, Ke
-
supporting information
p. 3649 - 3653
(2019/06/04)
-
- PPh3/I2/HCOOH: An efficient CO source for the synthesis of phthalimides
-
A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80 °C and furnishes the desired products in good to excellent yields.
- Wang, Yingying,Zhou, Yang,Lei, Min,Hou, Jinjun,Jin, Qinghao,Guo, Dean,Wu, Wanying
-
p. 1180 - 1185
(2019/01/26)
-
- Synthesis method of phthalimide and phenyl ring-substituted phthalimide derivative
-
The invention provides a synthesis method of phthalimide and a phenyl ring-substituted phthalimide derivative. The synthesis method comprises that aromatic ketone and ammonia gas or an ammonia gas precursor as substrates and air or oxygen as an oxygen source undergo a reaction under catalyst action and liquid phase conditions to produce phthalimide and a phenyl ring-substituted phthalimide derivative. The synthesis method is mild, realizes high oxidation efficiency and a high product yield, utilizes oxygen or air as an oxygen source, is economic and eco-friendly and has a good application prospect.
- -
-
Paragraph 0013; 0017; 0018; 0020; 0023; 0028
(2017/08/25)
-
- Cobalt-catalyzed direct carbonylation of aminoquinoline benzamides
-
A method for direct carbonylation of aminoquinoline benzamides has been developed. Reactions proceed at room temperature in trifluoroethanol solvent, use oxygen from air as an oxidant, and require Mn(OAc)3 as a cocatalyst. Benzoic and acrylic a
- Grigorjeva, Liene,Daugulis, Olafs
-
p. 4688 - 4690
(2015/01/08)
-
- MATRIX METALLOPROTEINASE INHIBITORS
-
The present invention relates to methyl sulfonamides and N-formamides derivatives of formula (I) and to processes for their syntheses. The invention also relates to pharmacological compositions containing these derivatives and methods of treating asthma, rheumatoid arthritis, COPD, rhinitis, osteoarthritis, psoriatie arthritis, psoriasis, pulmonary fibrosis, pulmonary inflammation, acute respiratory distress syndrome, perodontitis, multiple sclerosis, gingivitis, atherosclerosis, dry eye, neointimal proliferation which leads to restenosis and ischemic heart failure, stroke, renal disease, tumor metastasis, and other inflammatory disorders characterized by over expression and over activation of an matrix metalloproteinase using the compounds.
- -
-
Page/Page column 45
(2012/04/10)
-
- Carbon monoxide-free one-step synthesis of isoindole-1,3-diones by cycloaminocarbonylation of o-haloarenes using formamides
-
A new carbon monoxide-free, solvent-free, single step protocol for the synthesis of isoindole-1,3-diones from o-haloarenes using palladium acetate and xantphos catalysis is reported. The wider applicability of this protocol for several types of o-iodoarenes and a few o-bromoarenes makes it attractive. Aryl iodides and aryl bromides provided moderate to excellent yields of up to 93 %.
- Sawant, Dinesh N.,Wagh, Yogesh S.,Bhatte, Kushal D.,Bhanage, Bhalchandra M.
-
experimental part
p. 6719 - 6724
(2012/01/02)
-
- Inhibitors of dipeptidyl peptidase 8 and dipeptidyl peptidase 9. Part 2: Isoindoline containing inhibitors
-
To obtain selective and potent inhibitors of dipeptidyl peptidases 8 and 9, we synthesized a series of substituted isoindolines as modified analogs of allo-Ile-isoindoline, the reference DPP8/9 inhibitor. The influence of phenyl substituents and different P2 residues on the inhibitors' affinity toward other DPPs and more specifically, their potential to discriminate between DPP8 and DPP9 will be discussed. Within this series compound 8j was shown to be a potent and selective inhibitor of DPP8/9 with low activity toward DPP II.
- Van Goethem, Sebastiaan,Van der Veken, Pieter,Dubois, Veronique,Soroka, Anna,Lambeir, Anne-Marie,Chen, Xin,Haemers, Achiel,Scharpe, Simon,De Meester, Ingrid,Augustyns, Koen
-
scheme or table
p. 4159 - 4162
(2009/05/07)
-
- Metal-free and PdII-promoted [2+3] cycloadditions of a cyclic nitrone to phthalonitriles: Syntheses of oxadiazolines as well as phthalamide-PdII and dihydropyrrolyl-iminoisoindolinone-Pd II complexes with high catalytic activity in suzuki-miyaura cross-coupling reactions
-
The previously unknown reactions between phthalonitriles, 1,2-(CN) 2(C6)R1R2R3R4 1 (1a, R1 = R2 = R3 = R4 = H; 1b, R1 = R2 = R4 = H, R3 = CH 3; 1e, R1 = R4 = H, R2 = R 3 = Cl; 1d, R1 = R2 = R3 = R 4 = Cl; 1e, R1 = R2 = R3 = R 4 = F), and a cyclic nitrone, -O+ N=CHCH 2CH2CMe2 2, proceed under heating in a sealed tube to give phthalimides 3, 2-oxadiazolyl-benzonitriles 4 or ortho-bis(oxadiazolyl)tetrafluorobenzene 4e′. In the presence of palladium(II) chloride, phthalonitriles 1 react with 2 at room temperature, to give bis(pyrrolidin-2-ylidene)phthalamide PdII complexes 5 via metal-promoted rupture of the N-O bond of the oxadiazoline ring. The ketoimine ligands thus generated can be liberated from the metal by displacement with a diphosphine. Although the first [2+3] cycloaddition of 2 to 1 can occur in the absence of the metal to give the monocycloadducts 4, the second [2+3] coupling at the still-unreacted cyano group requires its activation by coordination to Pdc, affording complexes 6 containing two ligated oxadiazolyl-benzonitriles. These ligands undergo either i) further cycloaddition with 2 to afford ultimately (upon rearrangement) the bis(pyrrolidinylidene)phthalamide complexes 5 or ii) N-O bond cleavage in the oxadiazoline ring with intramolecular attack of the imine nitrogen on the cyano carbon and bridging to a second Pd II center to afford dimeric palladium(II) complexes 7, with chloride bridges, that bear a dihydropyrrolyl-iminoisoindolinone, a new type of ligand. The compounds were characterized by IR, 1H, and 13C NMR spectroscopy, ESI MS or FAB+ MS, elemental analyses and, in the case of 4c, 5 a, 5c, and 7c, also by X-ray diffraction analysis. Complexes 5a and 7c show high catalytic activity for the Suzuki-Miyaura cross-coupling reaction of bromobenzene and phenylboronic acid and give biphenyl in high yields with turnover frequencies (TOFs) of up to 9.0 × 105 h-1.
- Lasri, Jamal,Kopylovich, Maximilian N.,Da Silva, M. Fatima C. Guedes,Charmier, M. Adilia Januario,Pombeiro, Armando J. L.
-
experimental part
p. 9312 - 9322
(2009/09/06)
-
- COMPOUND INHIBITING DIPEPTIDYL PEPTIDASE IV
-
The invention aims to provide a dipeptidyl peptidase IV inhibitor which is satisfactory in respect of activity, stability and safety and has an excellent action as a pharmaceutical agent. The invention is directed to a compound represented by the following general formula or a pharmaceutically acceptable salt thereof: wherein R1 and R2 each represents hydrogen, an optionally substituted C1-6 alkyl group, or -COOR5 whereupon R5 represents hydrogen or an optionally substituted C1-6 alkyl group, or R1 and R2, together with a carbon atom to which they are bound, represent a 3- to 6-membered cycloalkyl group, R3 represents hydrogen or an optionally substituted C6-10 aryl group, R4 represents a hydrogen or a cyano group, D represents -CONR6-, -CO- or -NR6CO-, R6 represents hydrogen or an optionally substituted C1-6 alkyl group, E represents -(CH2)m- whereupon m is an integer of 1 to 3, -CH2OCH2-, or -SCH2-, n is an integer of 0 to 3, and A represents an optionally substituted bicyclic heterocyclic group or bicyclic hydrocarbon group.
- -
-
Page/Page column 27
(2010/02/14)
-
- NOVEL BENSOPHENONE DERIVATIVES OR SALTS THEREOF
-
A benzophenone derivative represented by the following formula: whereinR1 represents, for example, an optionally substituted heterocyclic group, or a substituted phenyl group; Z represents, for example, an alkylene group; R2 represents, for example, a carboxyl group optionally protected with alkyl;R3 represents, for example, an optionally protected hydroxyl group; R4 represents, for example, an optionally substituted cycloalkyloxy group; and R5 represents, for example, a hydrogen atom, ???or a salt thereof has anti-arthritic activity, inhibits bone destruction caused by arthritis, and provides high safety and excellent pharmacokinetics and thus is useful as therapeutic agent for arthritis. These compounds have inhibitory effect on AP-1 activity and are useful as preventive or therapeutic agent for diseases in which excessive expression of AP-1 is involved.
- -
-
-
- Structural elucidation of an oxidation product of sedimentary porphyrins by one-pot synthesis of 3-methylphthalimide
-
One-pot synthesis of 3-methylphthalimide was achieved from 1,2,3-trimethylbenzene. The starting compound was oxidized in two steps to produce methylphthalic acids. The o-isomer was converted into its anhydride, which was subjected to thermal reaction with urea to form 3-methylphthalimide. The product was identical with the reported oxidation product of sedimentary porphyrins.
- Nomoto,Kozono,Mita,Shimoyama
-
p. 1975 - 1976
(2007/10/03)
-
- Photochemical Additions of Alkenes to Phthalimides. Mechanistic Investigations on the Stereochemistry of Alkene Additions and the Effect of Aryl Substituents on the Regiochemistry of Alkene Additions
-
The mechanism of the photochemical addition of alkenes to phthalimides was investigated by determining the stereochemistry of the addition and the effect of aryl substituents on the regiochemistry.Intra- and intermolecular examples were examined.The stereochemistry of the addition of cis- and trans-2-butene to N-methylphthalimide to give 2,3,4-trimethyl-2-benzazepine-1,5-dione was studied.It was found that both alkenes added stereospecifically, each giving the corresponding cis- or trans-2,3,4-trimethyl-2-benzazepine-1,5-dione with >95percent stereospecificity.The mechanistic implication of this result is either that the photochemical addition is a concerted (2 + 2) addition or that any intermediate biradical closes faster than rotation around the C-C bond which would result in loss of stereochemistry.A second approach to this problem employed the directive effects of aryl substituents.The proposed biradical intermediate is similar in structure to the phthalimide radical anion.The directive effects of aryl substituents have been experimentally determined in this system and are consistent with theoretical predictions.Theoretical predictions for aryl-substituent directive effects in the alternative concerted (2 + 2) process are opposite to those for the biradical case, which predicts that donors will direct meta and acceptors para.Irradiation of 4-methoxy- and 4-carbomethoxy-N-methylphthalimide in the presence of 1-hexene afforded the benzazepinedione addition products that resulted from addition to the para and meta C(O)-N bonds, respectively.These results are entirely consistent with a concerted process.
- Mazzocchi, P. H.,Wilson, P.,Khachik, F.,Klingler, L.,Minamikawa, S.
-
p. 2981 - 2989
(2007/10/02)
-
