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77949676727
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A full account of the addition of organolithium. reagents to 19-ace-tylgnaphalin and related compounds will be disclosed in due course.
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A full account of the addition of organolithium. reagents to 19-ace-tylgnaphalin and related compounds will be disclosed in due course.
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62
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77949682741
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c-6=74.2ppm).
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c-6=74.2ppm).
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63
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0001751359
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H-18B=3.25 ppm) as a conse-quence of the triple-bond effect of the substituent at the 6ß-axial position. See
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H-18B=3.25 ppm) as a conse-quence of the triple-bond effect of the substituent at the 6ß-axial position. See: X Fayos, F. Fernández-Gadea, C. Pascual, A. Perales, F. Piozzi, M. Rico, B. Rodríguez, G. Savona, J. Org. Chem. 1984, 49, 1789.
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0000594734
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18B signal of which appeared at (5=3.78 ppm). See
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77949755172
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1H NMR spectra of precursors 12, 13, and 14 each featured a singlet at δ = 3.05-3.07 ppm attributable to the alkynyl proton. As expected, these signals were no longer seen in the spectra of the cor-responding dimers 21, 22, and 23.
-
1H NMR spectra of precursors 12, 13, and 14 each featured a singlet at (δ = 3.05-3.07 ppm attributable to the alkynyl proton. As expected, these signals were no longer seen in the spectra of the cor-responding dimers 21, 22, and 23.
-
-
-
-
67
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77949690566
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-
13C NMR signals corresponding to the terminal, alkynyl carbons in precursors 17, 19, and 20 at δ=78.3, 71.0, and 73.2 ppm are re-placed by signals attributable to the new quaternary sp carbons in 24, 25, and 26 at δ=74.4, 67.6, and 68.6 ppm, respectively.
-
13C NMR signals corresponding to the terminal, alkynyl carbons in precursors 17, 19, and 20 at (δ=78.3, 71.0, and 73.2 ppm are re-placed by signals attributable to the new quaternary sp carbons in 24, 25, and 26 at (δ=74.4, 67.6, and 68.6 ppm, respectively.
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68
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84890584287
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The bioorganometallic chemistry of ferrocene
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It should be noted that compounds 29b and 30b are new bioorgano-metallic derivatives, which have a ferrocene-triazole tether joining the two natural fragments. For the use of ferrocene derivatives in bioorganometallic chemistry, see: a (Ed.: P. Stepnicka), Wiley-VCH, Weinheim, A recent example
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It should be noted that compounds 29b and 30b are new bioorgano-metallic derivatives, which have a ferrocene-triazole tether joining the two natural fragments. For the use of ferrocene derivatives in bioorganometallic chemistry, see: a) N. Metzler-Nolte, M. Salmain, "The Bioorganometallic Chemistry of Ferrocene", in Ferrocene Ligands, Materials and Biomolecules (Ed.: P. Stepnicka), Wiley-VCH, Weinheim, 2008, pp. 499-639. A recent example:
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77949765891
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13CNMR spectra of dimers 29a-c, 30a, b, and 3.1 were almost identical to those of their precursors, except for the absence of the alkynyl proton signal and the appearance of signals attributa-ble to the tether and the newly formed triazole rings.
-
13CNMR spectra of dimers 29a-c, 30a, b, and 3.1 were almost identical to those of their precursors, except for the absence of the alkynyl proton signal and the appearance of signals attributa-ble to the tether and the newly formed triazole rings.
-
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71
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77949709500
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No traces of montanin A were detected in the experiments carried out in the course of this work. See ref. [22].
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No traces of montanin A were detected in the experiments carried out in the course of this work. See ref. [22].
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72
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77949663562
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+ ions, in agreement with the pro-posed structures.
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73
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The synthesis of some star-shaped amphiphilic derivatives of cholic acid using a click reaction has recently been reported: a for a recent review on the use of bile acids in synthesis, supramolecular/materials chemistry, and nanoscience, including molecular umbrellas, see
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The synthesis of some star-shaped amphiphilic derivatives of cholic acid using a click reaction has recently been reported: a) J. Luo, Y. Chen, X. X. Zhu, Synlett 2007, 2201;
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Hybrid macrocyclic scaffolds based on steroids are of special interest due to their structural pre-organization and flexibility; see: a
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Hybrid macrocyclic scaffolds based on steroids are of special interest due to their structural pre-organization and flexibility; see: a) A. L. Sisson, J. P. Clare, A. P. Davis, Chem. Commun. 2005, 5263;
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It is known that kinetically controlled processes frequently lead irre-versibly to the kinetic and statistical distribution of products, includ-ing a collection, of linear/cyclic oligomers and polymers of different chain lengths, thus inevitably resulting in poor yields of the desired macrocyclic structures. This is in contrast with the reversible reactions that form macrocycles under equilibrium conditions. In these cases, the thermodynamic stability allows the preparation of the macrocyclic target molecule, overcoming the formation of undesired by-products (dynamic covalent chemistry (DCC)), see
-
It is known that kinetically controlled processes frequently lead irre-versibly to the kinetic and statistical distribution of products, includ-ing a collection, of linear/cyclic oligomers and polymers of different chain lengths, thus inevitably resulting in poor yields of the desired macrocyclic structures. This is in contrast with the reversible reactions that form macrocycles under equilibrium conditions. In these cases, the thermodynamic stability allows the preparation of the macrocyclic target molecule, overcoming the formation of undesired by-products (dynamic covalent chemistry (DCC)), see: W. Zhang, J. S. Moore, Angew. Chem. 2006, 118, 4524;
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77949704007
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13C NMR spectra of compounds 41 and 44 showed four signals corresponding to the internal sp carbons at δ = 83.0, 74.5, 71.1, and 69.8 ppm and at δ = 83.4, 74.9, 71.1, and 70.4 ppm, respectively, confirming their identity as closed oligomeric structures of the precursor 43.
-
13C NMR spectra of compounds 41 and 44 showed four signals corresponding to the internal sp carbons at (δ = 83.0, 74.5, 71.1, and 69.8 ppm and at (δ = 83.4, 74.9, 71.1, and 70.4 ppm, respectively, confirming their identity as closed oligomeric structures of the precursor 43.
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94
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0002979617
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A cholic acid-based triply-bridged cyclophane showing moderate binding of organic guest molecules has been reported, see
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A cholic acid-based triply-bridged cyclophane showing moderate binding of organic guest molecules has been reported, see: S. Koh-moto, D. Fukui, T. Nagashima, K. Kishikawa, M. Yamamoto, K. J. Yamada, J. Chem. Soc. Chem. Commun. 1996, 1869.
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0042626308
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-1 for an alternating (3-up, 3-down) conformation and, therefore, are partially pre-organized, with the three arms oriented in the same direction. See: and references therein.
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-1 for an alternating (3-up, 3-down) conformation and, therefore, are partially pre-organized, with the three arms oriented in the same direction. See: K.J. Wallace, W. J. Belcher, D. R. Turner, K. R Syed, J. W. Steed, J. Am. Chem. Soc. 2003, 125, 9699, and references therein.
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77949750235
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6]DMSO at 90°C.
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6]DMSO at 90°C.
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97
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11444262571
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A. Vacca, C. Nativi, M. Cacciarini, R. Pergoli, S. Roelens, J. Am. Chem. Soc. 2004, 126, 16456.
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98
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77949691755
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2, RT) did not gener-ate the target product.
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2, RT) did not gener-ate the target product.
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-
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