- Synthesis of crystalline tetrahydro-beta-carboline
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The present invention relates to a method for preparing a tetrahydro-beta-carboline compound, which comprises a step of preparing a tetrahydro-beta-caboline compound by reacting a tryptamine compound and an aldehyde in an aqueous solution using a reaction accelerator containing a divalent acid. Accordingly, the method for preparing a tetrahydro-beta-carboline compound according to the present invention is an eco-friendly synthetic method that does not use an explosive organic solvent, but uses water as a solvent and tartaric acid which is a natural product as a reaction accelerator, thereby causing no environmental pollution; and requiring no separation process in addition to a simple filtering process since final products are crystals. Therefore, the method for preparing a tetrahydro-beta-carboline compound can be carried out in an industrially very simple and suitable process.
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Paragraph 0085-0089; 0095-0099; 0105-0109
(2021/03/23)
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- Design and synthesis of β-carboline and combretastatin derivatives as anti-neutrophilic inflammatory agents
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A series of β-carboline derivatives was synthesized by the Pictet-Spengler reaction with or without the combretastatin skeleton. The structures of these derivatives were elucidated by spectroscopic techniques. All synthesized compounds were evaluated for
- Kumar, Sunil,Wang, Yi-Hsuan,Chen, Po-Jen,Chang, Yu-Chia,Kashyap, Hemant K.,Shen, Ya-Ching,Yu, Huang-Ping,Hwang, Tsong-Long
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- Selectivity-tunable oxidation of tetrahydro-β-carboline over an OMS-2 composite catalyst: preparation and catalytic performance
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Controlling the reaction selectivity of organic transformations without losing high conversion is always a challenge in catalytic processes. In this work, a H3PO4·12WO3/OMS-2 nanocomposite catalyst ([PW]-OMS-2) was prepared through the oxidation of a Mn(ii) salt with sodium phosphotungstate by KMnO4. Comprehensive characterization indicates that different Mn2+precursors significantly affected the crystalline phase and morphology of the as-synthesized catalysts and only MnSO4·H2O as the precursor could lead to a cryptomelane phase. Moreover, [PW]-OMS-2 demonstrated excellent catalytic activity toward aerobic oxidative dehydrogenation of tetrahydro-β-carbolines due to mixed crystalline phases, enhanced surface areas, rich surface oxygen vacancies and labile lattice oxygen species. In particular, β-carbolines and 3,4-dihydro-β-carbolines could be obtained from tetrahydro-β-carbolines with very high selectivity (up to 99%) over [PW]-OMS-2viatuning the reaction solvent and temperature. Under the present catalytic system, scalable synthesis of a β-carboline was achieved and the composite catalyst showed good stability and recyclability. This work not only clarified the structure-activity relationship of the catalyst, but also provided a practical pathway to achieve flexible, controllable synthesis of functional N-heterocycles.
- Bi, Xiuru,Tao, Luyao,Yao, Nan,Gou, Mingxia,Chen, Gexin,Meng, Xu,Zhao, Peiqing
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supporting information
p. 3682 - 3692
(2021/03/22)
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- Asymmetric Biocatalytic Synthesis of 1-Aryltetrahydro-β-carbolines Enabled by “Substrate Walking”
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Stereoselective catalysts for the Pictet–Spengler reaction of tryptamines and aldehydes may allow a simple and fast approach to chiral 1-substituted tetrahydro-β-carbolines. Although biocatalysts have previously been employed for the Pictet–Spengler react
- Eger, Elisabeth,Iding, Hans,Kroutil, Wolfgang,Kuhn, Bernd,Schrittwieser, Joerg H.,Wetzl, Dennis
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p. 16281 - 16285
(2020/11/30)
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- Selective construction of alkaloid scaffolds by alcohol-based direct and mild aerobic oxidative Pictet-Spengler reactions
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Employing TBN/TEMPO as the catalysts and oxygen as the oxidant, the biologically and pharmaceutically significant tetrahydro-β-carboline and β-carboline alkaloid scaffolds that used to be obtained by multi-step processes can now be selectively obtained in only one-stepviadirect aerobic oxidative Pictet-Spengler reactions of tryptamines with alcohols under mild conditions, with water generated as the byproduct. In this reaction, TBN/TEMPO was interestingly found to be able to facilitate the cyclization step of the whole reaction. This method tolerates a variety ofC- andN-substituted tryptamines, and both the more reactive benzylic and allylic alcohols and the less reactive aliphatic alcohols. This method can also be extended to dihydro-β-carboline synthesis and applied to the more available and more economical tryptophan for β-carboline synthesis, revealing its broad substrate scope and potential in synthetic applications.
- Han, Feng,Li, Huan,Liu, Haicheng,Liu, Jianping,Xu, Qing
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supporting information
p. 7079 - 7085
(2020/10/02)
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- Organic base-promoted efficient dehydrogenative/decarboxylative aromatization of tetrahydro-β-carbolines into β-carbolines under air
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Organic base DBN has been identified as an efficient reagent for promoting the dehydrogenative/decarboxylative aromatization of tetrahydro-β-carbolines under air atmosphere, to access the corresponding β-carbolines in moderate to good yields. The utility of this protocol for the gram-scale synthesis of β-carboline alkaloids eudistomin U (7) and harmane (10) has also been demonstrated.
- Zhao, Ziquan,Sun, Yan,Wang, Lilin,Chen, Xuan,Sun, Yanpei,Lin, Long,Tang, Yulin,Li, Fei,Chen, Dongyin
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supporting information
p. 800 - 804
(2019/02/16)
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- Tetrahydro Beta-carboline derivative as well as preparation method and application of derivative
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The invention discloses a tetrahydro Beta-carboline derivative shown in a formula I as described in the specification, which is a novel compound with histone deacetylase inhibiting activity and can beused for treating some diseases with abnormally high expression of histone deacetylase effectively. The histone deacetylase is closely related to occurrence and development of cancers. The serial compounds can inhibit proliferation of tumor cells effectively by inhibiting the activity of the histone deacetylase and inducing differentiation and apoptosis of the tumor cells, so as to achieve the purpose of treating cancers.
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Paragraph 0060; 0113
(2018/04/26)
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- Dehydrogenation of N-Heterocycles by Superoxide Ion Generated through Single-Electron Transfer
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Nitrogen-containing heteroarene motifs are found in numerous pharmaceuticals, natural products, and synthetic materials. Although several elegant methods for synthesis of these compounds through dehydrogenation of the corresponding saturated heterocycles have been reported, some of the methods are hampered by long reaction times, harsh conditions, and the need for catalysts that are not readily available. This work reports a novel method for dehydrogenation of N-heterocycles. Specifically, O2.? generated in situ acts as the oxidant for N-heterocycle substrates that are susceptible to oxidation through a hydrogen atom transfer mechanism. This method provides a general, green route to N-heteroarenes.
- Huang, Yuan-Qiong,Song, Hong-Jian,Liu, Yu-Xiu,Wang, Qing-Min
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supporting information
p. 2065 - 2069
(2018/01/27)
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- Cu-catalyzed mild and efficient oxidation of THβCs using air: Application in practical total syntheses of perlolyrine and flazin
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A mild, efficient and environmentally benign method for synthesis of aromatic β-carbolines via Cu(ii)-catalyzed oxidation of 1,2,3,4-tetrahydro-β-carbolines (THβCs) was developed, in which air (O2) was used as the clean oxidant. This method has advantages such as environmentally friendliness, mildness, very good tolerance of functional groups, high yielding and easy experiment operation. In addition, this new methodology was successfully applied in the efficient and practical total syntheses of β-carboline alkaloids perlolyrine and flazin.
- Zheng, Bo,Trieu, Tien Ha,Meng, Tian-Zhuo,Lu, Xia,Dong, Jing,Zhang, Qiang,Shi, Xiao-Xin
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p. 6834 - 6839
(2018/02/23)
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- Synthesis and Investigation of Tetrahydro-β-carboline Derivatives as Inhibitors of the Breast Cancer Resistance Protein (ABCG2)
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The breast cancer resistance protein (ABCG2) transports chemotherapeutic drugs out of cells, which makes it a major player in mediating multidrug resistance (MDR) of cancer cells. To overcome this mechanism, inhibitors of ABCG2 can be used. Only a few potent and selective ABCG2 inhibitors have been discovered, i.e., fumitremorgin C (FTC), Ko143, and the alkaloid harmine, which contain a tetrahydro-β-carboline or β-carboline backbone, respectively. However, toxicity and or instability prevent their use in vivo. Therefore, there is a need for further potent inhibitors. We synthesized and pharmacologically investigated 37 tetrahydro-β-carboline derivatives. The inhibitory activity of two compounds (51, 52) is comparable to that of Ko143, and they are selective for ABCG2 over ABCB1. Furthermore, they are able to reverse the ABCG2-mediated resistance toward SN-38 and inhibit the ATPase activity. The cytotoxicity data show that their inhibitory effect is substantially higher than their toxicity.
- Spindler, Anna,Stefan, Katja,Wiese, Michael
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p. 6121 - 6135
(2016/07/26)
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- N-Bromo-succinimide promoted synthesis of β-carbolines and 3,4-dihydro-β-carbolines from tetrahydro-β-carbolines
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Herein, we report a facile synthesis of 3,4-dihydro-β-carbolines and aromatic β-carbolines from tetrahydro-β-carbolines, mediated by N-bromosuccinimide in toluene at 0°C to room temperature (rt), in good to moderate yields.
- Hati, Santanu,Sen, Subhabrata
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supporting information
p. 1040 - 1043
(2016/02/16)
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- An acid-free Pictet-Spengler reaction using deep eutectic solvents (DES)
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Deep eutectic solvents (such as the combination of either urea or glycerol with choline chloride) are effective solvents/organocatalysts for Pictet-Spengler condensations to form carbolines. The reaction conditions are quite mild and do not require additi
- Handy, Scott,Wright, Matthew
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p. 3440 - 3442
(2014/06/09)
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- Simple and efficient synthesis of tetrahydro-β-carbolines via the Pictet-Spengler reaction in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)
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1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) can act as both the solvent and the catalyst to promote the Pictet-Spengler reactions between tryptamine derivatives and aldehydes or activated ketones. For most substrates, removing the low boiling point HFIP by distillation directly afforded tetrahydro-β-carbolines in high yields.
- Wang, Li-Na,Shen, Su-Li,Qu, Jin
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p. 30733 - 30741
(2014/08/05)
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- Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst
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Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.
- Wendlandt, Alison E.,Stahl, Shannon S.
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supporting information
p. 506 - 512
(2014/01/23)
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- Mild and efficient cyanuric chloride catalyzed Pictet-Spengler reaction
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A practical, mild and efficient protocol for the Pictet-Spengler reaction catalyzed by cyanuric chloride (trichloro-1,3,5-triazine, TCT) is described. The 6-endo cyclization of tryptophan/tryptamine and modified Pictet-Spengler substrates with both electr
- Sharma, Ashish,Singh, Mrityunjay,Rai, Nitya Nand,Sawant, Devesh
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p. 1235 - 1242
(2013/07/26)
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- Comparative evaluation of a Pictet-Spengler protocol in microwave-assisted conversions of tryptamine with aryl- and carboxyaryl aldehydes: Role of ring strain in cyclocondensation of the primarily formed carboxyaryl-substituted β-carbolines
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An efficient microwave-assisted Pictet-Spengler protocol employing boric acid/acetic acid as a catalytic system was elaborated for the synthesis of 1-aryl-β-carbolines. Under the novel conditions tryptamine and 2-formylbenzoic acid furnished a pentacyclic
- Fodor, Kinga-Judit,Kocsis, Vasile-Ludovic,Kiss, Kolos,Karolyi, Benedek-Imre,Szabolcs, Armin,Silaghi-Dumitrescu, Luminita,Csampai, Antal
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p. 1381 - 1387
(2013/10/01)
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- Pictet-spengler reaction using ion-exchange resin as a catalyst and support for 'catch and release' purification
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The Pictet-Spengler reaction between tryptamine and aldehydes was catalyzed by Dowex 50W-X4 acidic ion-exchange resin. The products were obtained from the resin in high purity by 'catch and release' without the need for separate chromatographic purification.
- IzuMi, Minoru,Kido, Takeshi,Murakami, Miyu,Nakajima, Shuhei,Ganesan
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experimental part
p. 391 - 392
(2011/10/02)
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- Efficient and practical one-pot conversions of n- tosyltetrahydroisoquinolines into isoquinolines and of N-tosyltetrahydro-β- carbolines into β-carbolines through tandem β-elimination and aromatization
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An efficient, practical, and general method for conversions of N-tosyltetrahydroisoquinolines (N-tosyl-THIQs) into isoquinolines and of N-tosyltetrahydro-β-carbolines (N-tosyl-THBCs) into β-carbolines is described. Treatment of N-tosyl-THIQs or N-tosyl-THBCs with base in dimethyl sulfoxide afforded dihydroisoquinolines or dihydro-β-carbolines as intermediates, and these were then oxidized in situ by molecular oxygen to furnish isoquinolines or β-carbolines in good to high yields. Both one-pot conversions occurred through tandem β-elimination and aromatization. An efficient method for conversions ofN-tosyltetrahydroisoquinolines (N-tosyl-THIQs) and N-tosyltetrahydro-β-carbolines (N-tosyl-THBCs) into isoquinolines and β-carbolines is described. Treatment ofN-tosyl-THIQs or N-tosyl-THBCs with base affords dihydroisoquinolines or dihydro-β- carbolines. These can be oxidized in situ by molecular oxygen to furnish isoquinolines or β-carbolines. Copyright
- Dong, Jing,Shi, Xiao-Xin,Yan, Jing-Jing,Xing, Jing,Zhang, Qiang,Xiao, Sen
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experimental part
p. 6987 - 6992
(2011/02/24)
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- O-Benzenedisulfonimide as a reusable acid catalyst for an easy, efficient, and green synthesis of tetrahydroisoquinolines and tetrahydro-β-carbolines through Pictet-Spengler reaction
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The synthesis of tetrahydroisoquinolines and tetrahydro-β-carbolines, using the Pictet-Spengler reaction, was carried out in the presence of a catalytic amount of o-benzenedisulfonimide, which worked as a Br?nsted acid organocatalyst. The reaction conditi
- Barbero, Margherita,Bazzi, Stefano,Cadamuro, Silvano,Dughera, Stefano
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experimental part
p. 6356 - 6359
(2011/01/04)
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- SUBSTITUTED INDOLO-PIPERIDINE COMPOUNDS
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The present invention relates to substituted indolo-piperidine compounds and methods of synthesizing these compounds. The present invention also relates to pharmaceutical compositions containing substituted indolo-piperidine compounds and methods of treating cell proliferative disorders, such as cancer, by administering these compounds or pharmaceutical compositions to subjects in need thereof.
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Page/Page column 34
(2010/10/19)
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- Synthetic analogs of indole-containing natural products as inhibitors of sortase A and isocitrate lyase
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Guided by the inhibitory activities of indole-containing natural products against isocitrate lyase (ICL) from Candida albicans and sortase A (SrtA) from Staphylococcus aureus, a series of compounds structurally analogous to natural products were synthesized. Eight SrtA inhibitors and an ICL inhibitor having higher activities than the natural products were discovered by screening the enzyme inhibitory activities of synthesized compounds. Among the SrtA inhibitors discovered, six exhibited higher activities than p-hydroxymercuribenzoic acid, which suggests that these compounds have great potential as alternative antibacterial agents.
- Lee, Yeon-Ju,Han, Yu-Ri,Park, Wanki,Nam, Seo-Hee,Oh, Ki-Bong,Lee, Hyi-Seung
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scheme or table
p. 6882 - 6885
(2010/12/24)
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- Iodine-catalyzed highly effective pictet-spengler condensation: An efficient synthesis of tetrahydro-β-carbolines
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Molecular iodine was found to be an efficient catalyst for the two-component Pictet-Spengler condensation of tryptamine with aldehydes, which leads to the formation of tetrahydro-β-carbolines in high yields. Copyright Taylor & Francis Group, LLC.
- Prajapati, Dipak,Gohain, Mukut
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experimental part
p. 4426 - 4433
(2009/04/06)
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- Highly efficient Lewis acid-catalysed Pictet-Spengler reactions discovered by parallel screening
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High yielding Lewis acid-catalysed one-pot Pictet-Spengler reactions of tryptophan methyl ester and tryptamine with aliphatic and aromatic aldehydes were achieved in short reaction times with the aid of microwave irradiation.
- Srinivasan, Natarajan,Ganesan
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p. 916 - 917
(2007/10/03)
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- Pictet-Spengler reaction of nitrones and imines catalyzed by Yb(OTf)3-TMSCI
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The Pictet-Spengler reaction of nitrones and imines prepared from N-hydroxytryptamine and tryptamine gave the corresponding tetrahydro-β-carbolines in excellent yields in the presence of Yb(OTf)3-TMSCl in a mixture of CH2Cl2/su
- Tsuji, Riichiro,Yamanaka, Masamichi,Nishida, Atsushi,Nakagawa, Masako
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p. 428 - 429
(2007/10/03)
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- Mild Oxidation of 1,2,3,4-Tetrahydro-β-carbolines
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Oxidation of 1-(aryl or heteroaryl)-1,2,3,4-tetrahydro-β-carbolines (1a-r) with KMnO4 in dry THF afforded in the most cases almost exclusively 3,4-dihydro products (2) with a yield of 28-94percent.Only in few cases (1c, 1i, 1m) the reaction was non-selective and a significant amount of the fully aromatized products (3) (30-40percent of the reaction mixture) was observed.The influence of both the substituent nature and the substitution modes on the observed yield and selectivity of the reaction was discussed.Key words: 1,2,3,4-tetrahydro-β-carbolines, 3,4-dihydro-β-carbolines, selective oxidation, oxidation with KMnO4 in cold THF, substituent effect
- Mokrosz, M.J.,Paluchowska, M.H.,Misztal, S.
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p. 264 - 268
(2007/10/02)
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- Carbon-transfer Reactions with Heterocycles. Part 3. Synthetic Equivalence of Oxazolidines with Carbonyl Compounds
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Oxazolidines perform acid catalysed transfer of their C(2) units at the carbonyl group oxidation level to various nucleophiles, resulting in the synthesis of various heterocycles including some β-carboline and isoquinoline alkaloids.
- Singh, Harjit,Sarin, Rakesh
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p. 2623 - 2640
(2007/10/02)
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- Oxazolidines and thiazolidines as carbon transfer agents. Synthesis of tetrahydro-β-carboline and isoquinoline derivatives
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Oxazolidines and thiazolidines transfer their C2 units to appropiate nucleophiles and furnish the corresponding tetrahydro-β-carboline and isoquinoline derivatives
- Singh, Harjit,Sarin, Rakesh
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p. 107 - 110
(2007/10/02)
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- MODELS OF FOLATE COENZYMES-VIII AN APPROACH TO YOHIMBANE ALKALOIDS VIA CARBON-FRAGMENT TRANSFER FROM N5,N10-METHYLENETETRAHYDROFOLATE MODELS
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2-Substituted 1-tosyl-3,4,4-trimethylimidazolidines, prepared by the addition of anions to 1-tosyl-3,4,4-trimethyl-2-imidazolinium iodide 1, react with tryptamine in the presence of acetic acid to give 1-substituted β-carboline derivatives.The salt 1 reacts with anions of 2-CHR) to tryptamine to give pentacyclic products corresponding to the yohimbane skeleton.The product from 5c yields, after reduction of both the amide and the dithiane function, the precursor of epi- and allo-yohimbanes.
- Hiemstra, H. C.,Bieraeugel, H.,Wijnberg, M.,Pandit, U. K.
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p. 3981 - 3986
(2007/10/02)
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