- Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
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An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
- Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
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supporting information
p. 701 - 708
(2020/12/30)
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- Visible light-induced mono-bromination of arenes with BrCCl3
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A highly efficient and regioselective bromination of electron-rich arenes and heteroarenes using commercially available BrCCl3as a “Br” source has been developed. The reaction was performed in air under mild conditions with photocatalyst Ru(bpy)3Cl2·6H2O, avoiding the usage of strong acids and strong oxidants. Mono-brominated products were obtained with medium to excellent yields (up to 94%). This strategy has shown good compatibility and highpara-selectivity, which will facilitate the complicated synthesis.
- Fan, Jiali,Wei, Qiancheng,Zhu, Ershu,Gao, Jing,Cheng, Xiamin,Lu, Yongna,Loh, Teck-Peng
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supporting information
p. 5977 - 5980
(2021/06/18)
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- Synthesis method of 1-(4-bromophenyl) piperidine
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The invention discloses a preparation method of 1-(4-bromophenyl) piperidine, and belongs to the technical field of medical intermediates. Bromobenzene and piperidine are used as raw materials and react with potassium tert-butoxide or sodium tert-amyl alcohol in sulfolane in a heating mode to obtain N-phenyl piperidine; and then in the presence of a catalyst tetra-n-butyl tetraphenyl ammonium borate, a bromination reagent is added to react to obtain the 1-(4-bromophenyl)piperidine. The method is few in reaction steps, simple and convenient to operate and relatively high in yield, and a new path is provided for synthesis of the 1-(4-bromophenyl) piperidine.
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Paragraph 0028-0036
(2021/04/14)
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- Synthesis of some new distyrylbenzene derivatives using immobilized Pd on an NHC-functionalized MIL-101(Cr) catalyst: photophysical property evaluation, DFT and TD-DFT calculations
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In this study the catalytic application of a heterogeneous Pd-catalyst system based on metal organic framework [Pd-NHC-MIL-101(Cr)] was investigated in the synthesis of distyrylbenzene derivatives using the Heck reaction. The Pd-NHC-MIL-101(Cr) catalyst s
- Niknam, Esmaeil,Mahmoodi, Ali,Panahi, Farhad,Heydari Dokoohaki, Maryam,Zolghadr, Amin Reza,Khalafi-Nezhad, Ali
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p. 12374 - 12380
(2021/04/07)
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- COMPOUND SIMULTANEOUSLY INHIBITING LSD1 AND HDAC TARGETS AND APPLICATION THEREOF
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A compound having a general structural formula as shown in Formula I: X-AB-Y (Formula I); in the above Formula I, X is selected from any one of -CO2H, -CONHZ, -CH=CH-CO2H, -CH=CH-CONHZ, wherein Z is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted aryl, and hydroxyl; Y = -NR1R2, wherein NR1R2 is a substituted or unsubstituted 3- to 9-membered nitrogen-containing heterocycloalkyl; A and B are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted azaphenylene. The compound or corresponding pharmaceutical salt thereof can inhibit LSD1 and HDAC target proteins at the same time, thus inhibit the proliferation of many kinds of tumor cells and have good antitumor effect.
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Paragraph 0041; 0047-0048; 0052; 0055
(2020/11/26)
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- Redox-Neutral β-C(sp3)-H Functionalization of Cyclic Amines via Intermolecular Hydride Transfer
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Herein, we report the first redox-neutral and transition-metal-free β-C(sp3)-H functionalization of cyclic amines via a consecutive intermolecular hydride transfer process. A series of N-aryl pyrrolidines and N-aryl 1,2,3,4-tetrahydropyridines decorated with CF3 and carboxylic ester functionalities are directly accessed in good yields from pyrrolidines and piperidines. This work pushes forward the application of the intermolecular hydride transfer strategy in one-step assembly of molecular complexity.
- Zhou, Lan,Shen, Yao-Bin,An, Xiao-De,Li, Xian-Jiang,Li, Shuai-Shuai,Liu, Qing,Xiao, Jian
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supporting information
p. 8543 - 8547
(2019/11/03)
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- Electrochemical Regioselective Bromination of Electron-Rich Aromatic Rings Using n Bu 4 NBr
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Electrochemical regioselective bromination of electron-rich aromatic rings using stoichiometric tetrabutylammonium bromide (n Bu 4 NBr) has been accomplished under mild conditions. This protocol provides an environmentally friendly and simple way for the construction of C-Br bond in moderate to high yields with wide functional group tolerance.
- Bai, Ya,Che, Xin,Liu, Nian,Ning, Shulin,Shi, Lingling,Wang, Shutao,Wang, Siyu,Xiang, Jinbao,Xie, Wenxia
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supporting information
p. 1313 - 1316
(2019/06/20)
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- Practical and regioselective amination of arenes using alkyl amines
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The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.
- Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
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p. 426 - 433
(2019/05/01)
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- Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
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The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines.
- Vantourout, Julien C.,Law, Robert P.,Isidro-Llobet, Albert,Atkinson, Stephen J.,Watson, Allan J. B.
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p. 3942 - 3950
(2016/05/24)
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- GLUCOSYLCERAMIDE SYNTHASE INHIBITORS FOR THE TREATMENT OF DISEASES
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Described herein are compounds of Formula I, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or conditions associated with the enzyme glucosylceramide synthase (GCS).
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Paragraph 000835
(2015/04/15)
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- Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions
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An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.
- Zou, Qingzhu,Wang, Chao,Smith, Jen,Xue, Dong,Xiao, Jianliang
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supporting information
p. 9656 - 9661
(2015/06/30)
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- Copper-catalyzed electrophilic amination of arylsilanes with hydroxylamines
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A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl] dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.
- Miki, Yuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 172 - 175
(2013/03/28)
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- Synthesis of hindered anilines: Copper-catalyzed electrophilic amination of aryl boronic esters
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No longer a hindrance: Copper-catalyzed electrophilic amination of aryl boronic esters is accomplished under mild reaction conditions using 2.5-5.0 mol % of a catalyst derived from copper tert-butoxide and Xantphos ligand (see scheme). The reaction tolerates a wide range of functional groups and can be used to prepare some of the most hindered anilines made to date. Copyright
- Rucker, Richard P.,Whittaker, Aaron M.,Dang, Hester,Lalic, Gojko
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p. 3953 - 3956
(2012/06/04)
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- Copper-catalyzed amination of arylboronates with N,N-dialkylhydroxylamines
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A tolerant coupling: The title reaction has been developed to deliver arylamines (see scheme; Bz=benzoyl, dppbz=1,2-bis(diphenylphosphino)benzene). The catalysis is based on electrophilic, umpolung amination and enables the use of secondary acyclic amines. Various functional groups are tolerated, thus opening up a new substrate class for the Chan-Lam-type coupling.
- Matsuda, Naoki,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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p. 3642 - 3645
(2012/05/20)
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- Platinum/scandium-cocatalyzed cascade cyclization and ring-opening reaction of tertiary amines with substituted salicylaldehydes to synthesize 3-(aminoalkyl)coumarins
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The synthesis of 3-(aminoalkyl)coumarins starting with a platinum/scandium-cocatalyzed oxidative dehydrogenation of α,β- C(sp3)-H bonds of tertiary amines in the presence of ambient oxygen followed by reactions with substituted salicylaldehydes is revealed. The in situ formed enamines reacted with various salicylaldehydes, which resulted in the development of a one-pot synthetic protocol involving aldol reaction, cyclization, and then ring-opening.
- Xia, Xiao-Feng,Shu, Xing-Zhong,Ji, Ke-Gong,Shaukat, Ali,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information; experimental part
p. 342 - 345
(2011/03/19)
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- Platinum-catalyzed michael addition and cyclization of tertiary amines with nitroolefins by dehydrogenation of α,β-sp3 C-H bonds
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A mild platinum-catalyzed oxidative dehydrogenation of α,β- C(sp3)-H bonds of tertiary amines in the presence of ambient oxygen is revealed, and the in situ formed enamines subsequently reacting with various nitroolefins resulted in the development of two one-pot synthetic protocols involving Michael addition-elimination and Michael addition-cyclization. By using different functionalized nitroolefins compatible with the current oxidative conditions, two types of structurally divergent products, trisubstituted enamines and chromano[2,3-b]piperidines, could be expediently accessed, respectively.
- Xia, Xiao-Feng,Shu, Xing-Zhong,Ji, Ke-Gong,Yang, Yan-Fang,Shaukat, Ali,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information; experimental part
p. 2893 - 2902
(2010/07/09)
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- Selective functionalization of sp3 C - H bonds adjacent to nitrogen using (diacetoxyiodo)benzene (DIB)
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(Chemical Equation Presented) A PhI(OAc)2 mediated selective functionalization of sp3C - H bonds adjacent to a nitrogen atom has been reported. When piperidine derivates were used, direct diacetoxylation of α and β sp3 C - H adjacent to a nitrogen atom were observed to afford various cis-2,3-diacetoxylated piperidines. On the other hand, tetrahydroisoquinoline derivatives gave various α-C - H functionalized products in the presence of PhI(OAc)2. Nitroalkanes, dialkyl malonates, and β-keto ester are active participants in this coupling reaction. Meanwhile, α-amino nitriles can also be obtained by oxidative coupling of amineswithmalononitrile. 2009 American Chemical Society.
- Shu, Xing-Zhong,Xia, Xiao-Feng,Yang, Yan-Fang,Ji, Ke-Gong,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information; experimental part
p. 7464 - 7469
(2010/01/06)
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- Cu-Al hydrotalcite: An efficient and reusable ligand-free catalyst for the coupling of aryl chlorides with aliphatic, aromatic, and N(H)-heterocyclic amines
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Copper-aluminum hydrotalcite catalysts were effectively used in the coupling of aryl chlorides with aliphatic, aromatic, and N(H)-heterocyclic amines to afford the corresponding N-alkylated/arylated amines in excellent yields. The catalyst was quantitatively recovered from the reaction by simple filtration and reused for a number of cycles with almost consistent activity. Georg Thieme Verlag Stuttgart.
- Sreedhar,Arundhathi,Linga Reddy,Amarnath Reddy,Lakshmi Kantam
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experimental part
p. 2517 - 2522
(2010/03/24)
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- Aqueous-mediated N-alkylation of amines
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Direct N-alkylation of primary amines to secondary/tertiary amines and of secondary amines to tertiary amines has been achieved in excellent yields by employing alkyl, benzylic and allylic halides in the presence of NaHCO 3 in an aqueous medium at an elevated temperature. Amines of different stereoelectronic nature react with ease with different halides. The selective formation of secondary amines and the formation of three different substituted tertiary amines are some of the interesting features of this methodology. Reaction in an aqueous medium, operationally convenient conditions, excellent yields and innocuous byproducts, and the absence of transition-metal catalysts, expensive bases, solid supports and the formation of undesired quaternary ammonium salts makes this method a green chemical process. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Singh, Chingakham B.,Kavala, Veerababurao,Samal, Akshaya K.,Patel, Bhisma K.
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p. 1369 - 1377
(2008/09/17)
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- Scale-up of the green synthesis of azacycloalkanes and isoindolines under microwave irradiation
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A green approach to N-heterocyclization reactions ranging in scale from 20 mmol to 1 mol performed under microwave irradiation in open vessels has been investigated. By using water as the solvent and no transition metal catalysts, N-heterocycles are formed in a fraction of the time needed for conventional synthesis of these compounds. The obtained yields indicate that reactions can be performed at atmospheric pressure using the same reaction conditions as the corresponding sealed-vessel reactions. Single-mode and multimode microwave cavities have been used for open-vessel synthesis without changing reaction times producing similar yields.
- Barnard, T. Michael,Vanier, Grace S.,Collins Jr., Michael J.
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p. 1233 - 1237
(2012/12/23)
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- Aqueous N-heterocyclization of primary amines and hydrazines with dihalides: Microwave-assisted syntheses of N-azacycloalkanes, isoindole, pyrazole, pyrazolidine, and phthalazine derivatives
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The synthesis of nitrogen-containing heterocycles from alkyl dihalides (ditosylates) and primary amines and hydrazines via a simple and efficient cyclocondensation in an alkaline aqueous medium that occurs under microwave irradiation is described. This improved greener synthetic methodology provides a simple and straightforward one-pot approach to the synthesis of a variety of heterocycles, such as substituted azetidines, pyrrolidines, piperidines, azepanes, N-substituted 2,3-dihydro-1H-isoindoles, 4,5-dihydropyrazoles, pyrazolidines, and 1,2-dihydrophthalazines.
- Ju, Yuhong,Varma, Rajender S.
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p. 135 - 141
(2007/10/03)
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- Microwave-assisted amination from aryl triflates without base and catalyst
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(Equation presented) Aryl triflates are effectively converted to the corresponding anilines under microwave irradiation in 1-methyl-2-pyridone (NMP) without base and catalyst. Aryl triflates substituted with both electron-poor and electron-rich groups give good to excellent yields. It is noteworthy that the halogenated aryl triflates can chemoselectively react with amines to afford halogenated anilines.
- Xu, Gang,Wang, Yan-Guang
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p. 985 - 987
(2007/10/03)
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- 17β-amino and hydroxylamino-11β-arylsteroids and their derivatives having agonist or antagonist hormonal properties
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The invention is directed to a novel class of steroids which exhibit potent antiprogestational activity.
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- Palladium-catalyzed amination of aryl dibromides with secondary amines: Synthetic and mechanistic aspects
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Diaminobenzenes are obtained starting from m- and p-dibromobenzenes and secondary amines in the presence of Pd(dba)2/P(o-tolyl)3 and sodium tert- butoxide in moderate to good yields. Reductive dehalogenation of aryl dibromides is a major side reaction under these conditions. The study of this reaction has shown that the formation of reductive dehalogenation products occurs according to two independent ways. The first one proceeds via the well-known β-hydride elimination from amido-coordinated palladium complexes. The second one involves the formation of hydrido palladium complexes from amino-coordinated derivatives. Although our results do not allow us to propose a detailed mechanistic scheme, they clearly show that the deprotonation step of the catalytic amination cycle has a major effect on the amine/arene ratio.
- Beletskaya, Irina P.,Bessmertnykh, Alla G.,Guilard, Roger
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p. 6393 - 6397
(2007/10/03)
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- Surfactant Control of the Ortho/Para Ratio in the Bromination of Anilines. 2.
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We report the bromination of some N,N-disubstituted anilines (N-ethyl-N-methylaniline, N,N-diethylaniline, N-butyl-N-methylaniline, 1-phenylpyrrolidine, 1-phenylpiperidine) both in aqueous suspension of cetyltrimethylammonium tribromide (CTAB3) and in homogeneous solution (CHCl3).In the presence of surfactant we observed a regioselectivity different from that observed in homogeneous conditions.The regioselectivity seems to depend on the nature of the substituents on the nitrogen of the aniline as well as on the temperature.An explanation based on specific interactions between the aniline and the packed structure of the aggregate is proposed.
- Cerichelli, Giorgio,Mancini, Giovanna,Luchetti, Luciana
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p. 3797 - 3802
(2007/10/02)
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- Reductive one batch synthesis of N-arylpiperidines from primary amines and glutaraldehyde
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The construction of the piperidine ring about an aromatic nitrogen atom, by a 5C + N reductiye condensation reaction, using glutaraldehyde (pentanedial) and sodium borohydride in acidic water/methanol medium is described. The reaction is fast, affords good to excellent yields and appears insensitive to electronic effects and severe steric hindrance; it is found to be compatible with a large variety of aryl substituents, including nitro and oxo groups.
- Verardo,Giumanini,Favret,Strazzolini
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p. 447 - 450
(2007/10/02)
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- Aminobenzenes, XVII. Addition Products of N,N-Dialkylanilines and Bromine - Synthesis and Reactions
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4-Bromo-N,N-dialkylanilines 1 react with bromine in inert solvents to give the 1:1 addition compounds 2 or 3.IR and UV investigations established the structure of the isolated products to be CT complexes (? complexes) for 2 and N-bromoanilinium bromides for 3.The adducts 2 react to yield substitution products 6 and dealkylation products 7 in polar solvents (dimethylformamide, acetic acid, methanol), whereas the main product from 2a by reaction in acetone is N,N,N',N'-tetramethylbenzidine (9).Radical cations 10 are postulated to be the determining intermediates for these reactions.The tendency of the alkyl groups to be cleaved off decreases in the order isopropyl > ethyl > methyl.Under analogous conditions the N-bromo compounds 3 give predominantly the anilines 1 and only small amounts of substitution products 6, dealkylation and reaction to benzidines were not observed.
- Effenberger, Franz,Steinbach, Adalbert,Epple, Gerhard,Hanauer, Johann
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p. 3539 - 3551
(2007/10/02)
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