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For use in an annulation of 3-alkylindoles with 1,1-cyclopropanediesters, see: a
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For the reaction of cyclopropane-1,1-dicarboxylic acid diethyl ester with phenyl mercaptan to give homoconjugate product (2-phenylsulfanyl-ethyl)-malonic acid diethyl ester, see
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For the reaction of cyclopropane-1,1-dicarboxylic acid diethyl ester with phenyl mercaptan to give homoconjugate product (2-phenylsulfanyl-ethyl)-malonic acid diethyl ester, see: Stewart, J. M.; Westberg, H. H. J. Org. Chem. 1965, 30, 1951.
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0032963763
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The homoconjugate addition reactions of activated cyclopropane derivatives using β-keto esters as nucleophiles have to be performed under catalysis of ytterbium(III) trifluoromethanesulfonate at high pressures. See: Kotsuki, H, Arimura, K, Maruzawa, R, Ohshima, R. Synlett 1999, 650
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The homoconjugate addition reactions of activated cyclopropane derivatives using β-keto esters as nucleophiles have to be performed under catalysis of ytterbium(III) trifluoromethanesulfonate at high pressures. See: Kotsuki, H.; Arimura, K.; Maruzawa, R.; Ohshima, R. Synlett 1999, 650.
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19
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25844513623
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Srinivasulu, M.; Reddy, V. L. N.; Reddy, S. M.; Ravikanth, V.; Raju, T. V.; Ramakrishna, S.; Venkateswarlu, Y. Helv. Chim. Acta 2005, 88, 2527.
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Shi, M.; Tang, X.-Y.; Yang, Y.-H. J. Org. Chem. 2008, 73, 5311.
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Shi, M.1
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For recent reviews on organocatalysis, see: a
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For recent reviews on organocatalysis, see: (a) Barbas, C. F. III. Angew. Chem. Int. Ed. 2008, 47, 42.
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(b) List, B. Chem. Rev. 2007, 107, 5413.
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(c) Erkkilä, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416.
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(d) Mukherjee, S.; Yang, J. W.; Hoffmann, S.; List, B. Chem. Rev. 2007, 107, 5471.
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For additional examples, see (a) Halland, N.; Hansen, T.; Jøgensen, K. A. Angew. Chem. Int. Ed. 2003, 42, 4955.
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35
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0001270236
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Nucpeophilic ring opening of cyclopropyl ketones by thiophenoxide anion has been known by Anand. See
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Nucpeophilic ring opening of cyclopropyl ketones by thiophenoxide anion has been known by Anand. See: Anand, R. C.; Ranjan, H. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1985, 24, 673.
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Anand, R.C.1
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36
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24944565175
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For example, benzothiepine derivatives have been reported to show activity as apical sodium-codependent bile acid transporter for use in the treatment of hyperlipidemic conditions and CCR5 antagonists as anti-HIV-1 agents. See: (a) Tremont, S. J.; Lee, L. F.; Huang, H.-C.; Keller, B. T.; Banerjee, S. C.; Both, S. R.; Carpenter, A. J.; Wang, C.-C.; G arland, D. J.; Huang, W.; Jones, C.; Koeller, K. J.; Kolodziej, S. A.; Li, J.; Manning, R. E.; Mahoney, M. W.; Miller, R. E.; Mischke, D. A.; Rath, N. P.; Fletcher, T.; Reinhard, E. J.; Tollefson, M. B.; Vernier, W. F.; Wagner, G. M.; Rapp, S. R.; Beaudry, J.; Glenn, K.; Regina, K.; Schuh, J. R.; Smith, M. E.; Trivedi, J. S.; Reitz, D. B. J. Med. Chem. 2005, 48, 5837.
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For example, benzothiepine derivatives have been reported to show activity as apical sodium-codependent bile acid transporter for use in the treatment of hyperlipidemic conditions and CCR5 antagonists as anti-HIV-1 agents. See: (a) Tremont, S. J.; Lee, L. F.; Huang, H.-C.; Keller, B. T.; Banerjee, S. C.; Both, S. R.; Carpenter, A. J.; Wang, C.-C.; G arland, D. J.; Huang, W.; Jones, C.; Koeller, K. J.; Kolodziej, S. A.; Li, J.; Manning, R. E.; Mahoney, M. W.; Miller, R. E.; Mischke, D. A.; Rath, N. P.; Fletcher, T.; Reinhard, E. J.; Tollefson, M. B.; Vernier, W. F.; Wagner, G. M.; Rapp, S. R.; Beaudry, J.; Glenn, K.; Regina, K.; Schuh, J. R.; Smith, M. E.; Trivedi, J. S.; Reitz, D. B. J. Med. Chem. 2005, 48, 5837.
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37
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8844238461
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(b) Seto, M.; Aramaki, Y.; Okawa, T.; Miyamoto, N.; Aikawa, K.; Kanzaki, N.; Niwa, S.; Iizawa, Y.; Baba, M.; Shiraishi, M. Chem. Pharm. Bull. 2004, 52, 577.
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Seto, M.1
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8844265387
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(c) IkemotoT, ; Ito, T.; Nishiguchi, A.; Tomimatsu, K. Tetrahedron 2004, 48, 10851.
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IkemotoT1
Ito, T.2
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Tomimatsu, K.4
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39
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67649988911
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13C NMR, and MS).
-
13C NMR, and MS).
-
-
-
-
40
-
-
67649998260
-
-
+.
-
+.
-
-
-
-
41
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67649970280
-
-
Typical procedure for the tandem synthesis of benzo[b]-thiepines 6 was operated as described in ref. 14, except for replacing benzenethiols 2 with o-salicylaldehydes 5. The reaction gave 6 as off-white crystal solids. All new compounds have been isolated in pure form and characterized by spectral data (1H NMR, 13C NMR, and MS, Selected Data for Compounds 6 Compound 6e: yield 56, mp 120, 121 °C. 1H NMR (400 MHz, CDCl 3, δ, 9.62 (1 H, s, CHO, 7.40, 6.84 (8 H, m, ArH, and CH=C, 4.26 (1 H, dd, J, 3.2, 11.4 Hz, SCH, 3.79 (3 H, s, OCH 3, 3.26, 3.02 (2 H, m, CH2, 2.37 (3 H, s, CH 3, 13C NMR 100 MHz, CDCl3, δ, 194.9, 159.0, 150.4, 141.8, 137.5, 136.0, 135.2, 134.7, 134.5, 132.9, 130.9, 128.0, 114.2, 55.4, 52.6, 37.3, 21.0. ESI-HRMS: m/z calcd for C 19H18O2S: 310
-
2S: 310.1028; found: 310.1031.
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-
-
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42
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33750307526
-
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For remarkable examples, see: a
-
For remarkable examples, see: (a) Rios, R.; Sunden, H.; Ibrahem, I.; Zhao, G.-L.; Eriksson, L.; Cordova, A. Tetrahedron Lett. 2006, 47, 8547.
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Rios, R.1
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Eriksson, L.5
Cordova, A.6
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43
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33747594792
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(b) Wang, W.; Li, H.; Wang, J.; Zu, L. J. Am. Chem. Soc. 2006, 128, 10354.
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34250714916
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(c) Ibrahem, I.; Sunden, H.; Rios, R.; Zhao, G.-L.; Cordova, A. Chimia 2007, 61, 219.
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Ibrahem, I.1
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Cordova, A.5
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45
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67649995137
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-
For comparision, we also conducted the tandem reaction with the 'best' substrate 1c under Anand's condition (ref. 12). After refuxing in EtOH for 3 h, the reaction afforded a mixture of products, from which 6g was isolated in 13% yield.
-
For comparision, we also conducted the tandem reaction with the 'best' substrate 1c under Anand's condition (ref. 12). After refuxing in EtOH for 3 h, the reaction afforded a mixture of products, from which 6g was isolated in 13% yield.
-
-
-
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46
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67649998261
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-
Enantiomeric excess was determined chromatographically as follows: Diacel CHIRALPAK AS-H, hexane - 2-PrOH (80:20), flow rate 0.6 mL/min, λ = 254 nm.
-
Enantiomeric excess was determined chromatographically as follows: Diacel CHIRALPAK AS-H, hexane - 2-PrOH (80:20), flow rate 0.6 mL/min, λ = 254 nm.
-
-
-
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47
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67649939088
-
-
2 - n-hexane. Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 726088.
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2 - n-hexane. Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 726088.
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48
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0001123797
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Arai, I.; Mori, A.; Yamamoto, H. J. Am. Chem. Soc. 1985, 107, 8254.
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