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c) For a review of efforts aimed at diazonamide synthesis (through 2001) see: T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2494;
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19
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0242276704
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note
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Ring closure in 5 could also occur via its phenol tautomer.
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20
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0242308553
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note
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Geometry optimization of 6 (R = Ac) was performed by using the Amber force field within Macromodel v7.0 (Schrödinger). The result was subjected to a Monte Carlo molecular dynamics simulation. Figure 1 depicts rigid superimposition of the ten lowest energy conformations calculated from this exercise.
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Prepared in two steps from 7-bromoindole and methyl 3-bromopyruvate oxime. See: a) Y. Konda-Yamada, C. Okada, K. Yoshida, Y. Umeda, S. Arima, N. Sato, T. Kai, H. Takayanagi, Y. Harigaya, Tetrahedron 2002, 58, 7851-7861;
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Ph.D. thesis, Harvard University
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0242276706
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note
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2; 2) KOH, aq MeOH (70%-2 steps).
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30
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0242371503
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note
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C11 stereochemistry, relative to C10, is governed by geometry. Only two cis-fused dihydrobenzofuro[2,3b] indole diastereomers are formed. C10-(R), C11-(S) diastereomer 15 has been characterized by X-ray diffraction (Scheme 2). CCDC-218220 (15) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.a-c.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223-336-033; or deposit@ccdc.cam.ac.uk).
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31
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0242371506
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2O gradient) but partially degrade during flash chromatography on silica gel.
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2. > 95% yield).
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0242371499
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note
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We are grateful to Professor William Fenical (Scripps Oceanographic Institute) for a generous gift of natural (-)-diazonamide A.
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