synthesis and catalytic functionalization of biologically active indoles

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1 Palladium-catalyzed Coupling Reactions of Indoles 51 2- and 3-bromo-N-methylindoles catalyzed by P(tert-Bu)3 and Pd(dba)2. To prevent competition between the reacting amine and indole N-H, N-methylindoles were used instead of the parent indoles. The reactions of 2- and 3-bromo-Nmethylindoles with N-methylaniline (Table 8, entries 1 and 3) occurred at room temperature whereas reactions of 2- and 3-bromo-N-methylindoles with diphenylamine (Table 8, entries 2 and 4) occurred at 100 °C. Non reaction of these bromoindoles were observed with primary or secondary alkylamines and with primary arylamines. Further palladium-catalyzed aminations were listed in this publication and proceeded with a range of electron-rich heteroaromatic bromides and chlorides with certain classes of amines. Table 8. Amination of indole bromides with Pd(dba)2/PtBu3. Ar-Br HNRR´ Pd(dba) 2/PtBu 3 NaOtBu toluene Ar-NRR´ Entry Ar-Br Amine Product Cond. Yield [%] 1 N Me Br 2 N Me Br 3 4 Br N Me Br N Me HNMePh N Me NMePh rt, 16 h 83 HNPh2 N Me NPh2 HNMePh HNPh2 NMePh N Me NPh 2 N Me 100 °C, 16 h 86 rt, 16 h 70 100 °C, 16 h 71
1 Palladium-catalyzed Coupling Reactions of Indoles 52 Beletskaya and co-workers examined the possibility of applying nitrogencontaining groups (amino, amido, ureido) into halogen-substituted indoles, benzofurans and tetrahydro-carbazoles. [125] Following Scheme 42 demonstrates selective examples of the palladium-catalyzed amination of bromoindoles with amines. Br MeO Br MeO Br 162 163 163 N Me CO 2Et Me N Me CO 2Et Me N Me N H H 2N O NH 2 Pd 2(dba) 3 (1-2 mol%) (tBu 2)BP-phos (3-6 mol%) tBuONa (1.4 equiv) toluene, 100 °C, 5 h Pd 2(dba) 3, 3,5-(CF 3) 2Xantphos dioxane, 100 °C EtO 2C MeO Scheme 42. Palladium-catalyzed amination of 5- and 6-bromo-indole. Me H N N Me N MeO 164 (83%) N 165 (53%) MeO H N O N Me 166 (91%) N Me CO 2Et Me N Me CO 2Et Bromoindoles having no substituent on the nitrogen atom did not undergo the palladium-catalyzed amination reaction. Additionally they observed quantitative removal of acetyl and phenylsulfonyl protecting groups so that these substrates could not be used in amination reaction as well. The authors succeeded in obtaining the target product 164 in 83% yield by coupling indole 162 with piperidine using Pd2(dba)3 (1 mol%) as catalyst, (tert- Bu2BP-phos) (3 mol%) as ligand and tert-BuONa as base in toluene at 100 °C in 5 h. The amount of palladium catalyst was increased to 2 mol% (tert-BuONa, 6 mol%) to attain moderate yield of amination product 165 (53%) in 10 h in the less smooth reaction with bromomindole 163. Me
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Leibniz-Institut für Katalyse e. V
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Für meine Eltern Siegfried und Ker
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Mein besonderer Dank gilt Dr. Anneg
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Table of Contents Preface .........
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List of Abbreviations Ac Acetyl aq
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PAPER Coupling Reactions of Electro
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3 Publications 108 3.5 Synthesis of
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Scheme 2 Ti-catalyzed synthesis of
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mixture was used for the synthesis
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7.11 (ddd, 1H, J = 8.0 Hz, J = 7.0
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FULL PAPER DOI: 10.1002/ejoc.200800
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Synthesis of Potential 5-HT 6 Recep
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FULL PAPER DOI: 10.1002/ejoc.200700
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Synthesis of Indole-2,3-dicarboxyla
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3 Publications 132 3.8 Selective Re
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8 7 N R N R OH CO2Et CO2Et OH indol
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mixture was stirred at 78 C for 3 m
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3.89 (s, 2H, H-10), 4.27 (s, 2H, H-
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DOI: 10.1002/cssc.200700160 General
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Zn-Catalyzed Hydroamination of Term
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Zn-Catalyzed Hydroamination of Term
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3 Publications 146 3.10 Zn-Catalyze
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Over the past years, we investigate
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3 Publications 150 3.11 First Synth
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4608 K. Alex et al. / Tetrahedron L
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Publikationen 1 Titanium-Catalyzed
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synthesis and catalytic functionalization of biologically active indoles

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