- Method for promoting acylation of amine or alcohol by carbon dioxide
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The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
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Paragraph 0033-0034
(2021/05/29)
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- Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
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Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
- Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
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- Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
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A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
- Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
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p. 1487 - 1494
(2019/02/16)
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- Carbonylation of C?N Bonds in Tertiary Amines Catalyzed by Low-Valent Iron Catalysts
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The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low-valent iron complexes, including K2[Fe(CO)4], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).
- Nasr Allah, Tawfiq,Savourey, Solène,Berthet, Jean-Claude,Nicolas, Emmanuel,Cantat, Thibault
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supporting information
p. 10884 - 10887
(2019/07/15)
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- Carbonylative Coupling of Alkyl Zinc Reagents with Benzyl Bromides Catalyzed by a Nickel/NN2 Pincer Ligand Complex
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An efficient catalytic protocol for the three-component assembly of benzyl bromides, carbon monoxide, and alkyl zinc reagents to give benzyl alkyl ketones is described, and represents the first nickel-catalyzed carbonylative coupling of two sp3-carbon fragments. The method, which relies on the application of nickel complexed with an NN2-type pincer ligand and a controlled release of CO gas from a solid precursor, works well with a range of benzylic bromides. Mechanistic studies suggest the intermediacy of carbon-centered radicals.
- Andersen, Thomas L.,Donslund, Aske S.,Neumann, Karoline T.,Skrydstrup, Troels
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supporting information
p. 800 - 804
(2017/12/26)
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- Nickel and Nucleophilic Cobalt-Catalyzed Trideuteriomethylation of Aryl Halides Using Trideuteriomethyl p-Toluenesulfonate
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Herein, a novel approach for the trideuteriomethylation of aryl halides using nickel and nucleophilic cobalt catalysts and the readily available trideuteriomethyl p-toluenesulfonate (CD3OTs) is described. This method provides access to a wide r
- Komeyama, Kimihiro,Yamahata, Yuta,Osaka, Itaru
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supporting information
p. 4375 - 4378
(2018/07/29)
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- Thermolysis and radiofluorination of diaryliodonium salts derived from anilines
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Aniline-derived diaryliodonium salts were synthesized and functionalized in good to excellent yields by judicious utilization of electron-withdrawing protecting groups. This simple approach opens another route to radiolabeling amino arenes in relatively complex molecules, such as flutemetamol.
- Linstad, Ethan J.,Vāvere, Amy L.,Hu, Bao,Kempinger, Jayson J.,Snyder, Scott E.,DiMagno, Stephen G.
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supporting information
p. 2246 - 2252
(2017/03/17)
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- The copper-catalyzed aerobic oxidative amidation of tertiary amines
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A general and efficient method for the synthesis of tertiary amides has been developed via the copper-catalyzed aerobic oxidative amidation of tertiary amines. Due to the use of the O2 oxidant, various functional groups were well tolerated under the present conditions. Extensive substrates studies demonstrated its potential as a practical approach for the synthesis of tertiary amides.
- Cheng, Hui-Cheng,Hou, Wen-Jun,Li, Zeng-Wen,Liu, Ming-Yu,Guan, Bing-Tao
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supporting information
p. 17596 - 17599
(2015/12/08)
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- Iron-catalyzed aerobic oxidative amidation of tertiary amines with carboxylic acids
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An oxidative amidation of tertiary amines with carboxylic acids has been developed in the presence of FeCl3·6H2O as catalyst and oxygen as oxidant. A variety of tertiary amides were obtained in good to excellent yields from inexpensive and readily available reagents. The possible reaction pathways were investigated.
- Ma, Lina,Li, Yuanming,Li, Zhiping
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p. 1310 - 1315
(2015/03/18)
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- Direct oxidative amidation between N,N-dimethylanilines and anhydrides using metal-organic framework [Cu2(EDB)2(BPY)] as an efficient heterogeneous catalyst
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A crystalline porous metal-organic framework [Cu2(EDB) 2(BPY)] was synthesized and used as a heterogeneous catalyst for the direct oxidative amidation between N,N-dimethylanilines and anhydrides to form tertiary amides as the principal products. The [Cu2(EDB) 2(BPY)] exhibited similar activity as compared to that of [Cu 2(BDC)2(BPY)], [Cu2(BDC)2(DABCO)], MOF-143, and other common homogeneous salt catalysts. The optimal reaction conditions employed were [Cu2(EDB)2(BPY)] (10 % mol), TBHP (2 equiv), pyridine (1 equiv) in CH3CN at 80 °C over 2 h. The Cu2(EDB)2(BPY) could be separated from the reaction mixture by filtration, and could be recovered and reused several times without a significant degradation in catalytic activity and selectivity. Furthermore, generality of the optimal conditions was confirmed by employing various N,N-dimethylaniline and anhydride derivatives. Copyright
- Dang, Giao H.,Nguyen, Thanh D.,Le, Dung T.,Truong, Thanh,Phan, Nam T.S.
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p. 1129 - 1137
(2014/11/12)
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- Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides
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A general and efficient method for amide bond synthesis has been developed. The method allows for synthesis of tertiary amides from readily available tertiary amines and anhydrides in the presence of FeCl2 as catalyst and tert-butyl hydroperoxide in water (T-Hydro) as oxidant. Mechanistic studies indicated that the in situ-generated α-amino peroxide of tertiary amine and iminium ion act as key intermediates in this oxidative transformation.
- Li, Yuanming,Ma, Lina,Jia, Fan,Li, Zhiping
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p. 5638 - 5646
(2013/07/26)
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- Copper-catalyzed N-methylation of amides and O-methylation of carboxylic acids by using peroxides as the methylating reagents
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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
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supporting information
p. 3326 - 3329
(2013/07/26)
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- Mild chemical and biological synthesis of donor-acceptor flanked reporter stilbenes: Demonstration of a physiological wittig olefination reaction
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Unprecedented chemoselectivity is reported for the Wittig olefination reaction leading to the formation of reporter stilbenes under physiological conditions.
- McLeod, David,McNulty, James
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supporting information
p. 6127 - 6131,5
(2020/09/16)
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- Hydrosilanes are not always reducing agents for carbonyl compounds, II: Ruthenium-catalyzed deprotection of tert-butyl groups in carbamates, carbonates, esters, and ethers
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Hydrosilanes act as a reagent to cleave the C-O bond of OtBu groups in carbamates, carbonates, esters, and ethers by catalysis of a triruthenium cluster. The reaction offers a novel deprotection method, for OiBu groups under neutral conditions, showing unique selectivities that have never been accomplished with conventional Bronsted or Lewis acidic promoters. Possible mechanisms for C-O cleavage are discussed on the basis of NMR spectroscopic analysis.
- Hanada, Shiori,Yuasa, Akihiro,Kuroiwa, Hirotaka,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 1021 - 1025
(2010/04/27)
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- COMPOSITIONS CONTAINING, METHODS INVOLVING, AND USES OF NON-NATURAL AMINO ACIDS AND POLYPEPTIDES
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Disclosed herein are non-natural amino acids and polypeptides that include at least one non-natural amino acid, and methods for making such non-natural amino acids and polypeptides. The non-natural amino acids, by themselves or as a part of a polypeptide, can include a wide range of possible functionalities, but typical have at least one aromatic amine group. Also disclosed herein are non-natural amino acid polypeptides that are further modified post-translationally, methods for effecting such modifications, and methods for purifying such polypeptides. Typically, the modified non-natural amino acid polypeptides include at least one alkylated amine group. Further disclosed are methods for using such non-natural amino acid polypeptides and modified non-natural amino acid polypeptides, including therapeutic, diagnostic, and other biotechnology uses.
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Page/Page column 172; 13/40
(2008/06/13)
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- Amide conformational switching induced by protonation of aromatic substituent
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(Matrix presented) Introduction of an electron-withdrawing group on the aromatic ring of N-methylacetanilide decreased the ratio of the cis conformer, and the ratio correlates well with the Hammett σ values of the substituents. These steric properties can be applied to achieve amide conformational swiching by protonation at the aromatic substituent of 4-[bis(dimethylamino)]-N-methylacetanilide or N-[p-(dimethylamino)phenyl]-N-phenylacetamide.
- Yamasaki, Ryu,Tanatani, Aya,Azumaya, Isao,Saito, Shoichi,Yamaguchi, Kentaro,Kagechika, Hiroyuki
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p. 1265 - 1267
(2007/10/03)
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- Oxidative Dealkylation of 4-Substituted N,N-Dialkylanilines with Molecular Oxygen in the Presence of Acetic Anhydride Promoted by Cobalt(II) or Copper(I) Chloride
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The reaction of 4-substituted N,N-dimethylanilines 1a-d with acetic anhydride 5 proceeded efficiently in the presence of a catalytic amount of cobalt(II) or copper(I) chloride under oxygen to give the corresponding N-methylacetanilides 2a-d along with N-methylformanilides 3a-d.The reaction of N-alkyl-N-methyl-p-toluidines 1f-h with cobalt chloride revealed that the order of reactivity of the N-substituents follows the sequence allyl > benzyl >/= methyl > ethyl, while in the case of copper chloride the order was benzyl > allyl > methyl > ethyl.Aldehydes 18a-e and phenylglyoxylic acid derivatives 18f and 18g were obtained in fair to good yield from the reaction of n-substituted N-ethyl-p-toluidines 17a-g.
- Murata, Satoru,Suzuki, Kaoru,Tamatani, Akira,Miura, Masahiro,Nomura, Masakatsu
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p. 1387 - 1392
(2007/10/02)
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- Cobalt(II) Chloride Catalyzed Oxidation of 4-Substituted N,N-Dialkylanilines with Molecular Oxygen in the Presence of Acetic Anhydride
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The oxidation of 4-substituted N,N-dialkylanilines with molecular oxygen using a catalytic amount of cobalt(II) chloride efficiently proceeds in the presence of acetic anhydride to give N-alkylacetanilides in good yields along with N-alkylformanilides.
- Murata, Satoru,Tamatani, Akira,Suzuki, Kaoru,Miura, Masahiro,Nomura, Masakatsu
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p. 757 - 760
(2007/10/02)
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- ipso Nitration. XXVIII. Nitration of 4-substituted toluenes: 1,2 adducts
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Nitration of 4-acetamido, 4-chloro, and 4-methoxy-toluene in acetic anhydride gives in each case a cis 1,2 nitronium acetate adduct in adition to the nitro substitution product(s).Nitration of 4-fluorotoluene gives a pair of diastereomeric 1,4 nitronium acetate adducts and the cis 1,2 adduct.
- Fisher, Alfred,Fyles, Deborah L.,Henderson, George, N.,Mahasay, Sumit Ray
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p. 1764 - 1770
(2007/10/02)
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- Meta Functionalization of Anilines and Phenol
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Base-promoted proton abstraction from ?-(N-tert-butyldimethylsilyl-N-methylaniline)chromium tricarbonyl (3) took place predominantly at the meta position and variously meta-substituted N-methylacetanilides 4 were obtained after reactions with electrophiles followed by oxidative decomplexation and N-acetylation.Application of the present method to variously N,N-disubstituted anilines 5 and phenols 7 was then examined and the corresponding meta substituted anilines 6 and phenol 9 were obtained.Keywords - metalation of aromatic ring; chromium tricarbonyl complex; tert-butyl dimethylsilyl protecting group; meta-substituted anilines; meta-substituted phenol; electrophilic substitution
- Fukui, Mineo,Ikeda, Toshiya,Oishi, Takeshi
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p. 466 - 475
(2007/10/02)
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- AN ANOMALOUS DEALKYLATION-ACYLATION OF N,N-DIALKYLANILINES
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N,N-Dialkylaniline undergoes a thermal N-dealkylation and acylation in the presence of 2-acetoxypyridines.
- Newkome, George R.,Yuanjiao, Xia
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p. 981 - 982
(2007/10/02)
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- META FUNCTIONALIZATION OF ANILINES AND PHENOL
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Regioselective introduction of various functional groups on the meta-position of anilines and phenol was achieved by proton abstraction from chromium tricarbonyl complexes 3,5,7 with n-BuLi, followed by the addition of electrophiles and decomplexation.
- Fukui, Mineo,Ikeda, Toshiya,Oishi, Takeshi
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p. 1605 - 1608
(2007/10/02)
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