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0027305949
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For an efficient approach to the ethenyl-bridged derivatives, see: King, A. O.; Corley, E. G.; Anderson, R. K.; Larsen, R D.; Verhoeven, T. R.; Reider, P. J.; Xiang, Y. B.; Eelley, M.; Leblanc, Y.; Labelle, M.; Prasit, P.; Zamboni, R. J. J. Org. Chum. 1993, 58, 3731.
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(b) A shorter approach could be the selective reduction of chlorophthalic anhydride; no success was obtained with this procedure. For an example of this method see: Taub, D.; Girotra, N. N.; Hoffsommer, R. D.; Kuo, C H.; Slates, H. L.; Weber, S.; Wendler, N. L. Tetrahedron 1968, 24, 2443.
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For a list of other benzaldehyde-related ortho directing groups see ref 8
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Directed ortho metalation of the cyclohexylimine of 4-chlorobenzaldehdye only provided BuLi attack at the imine and no detectable ortho lithiation. Ortho lithiation of the cyclohexylimines is reported to work only with aryl groups with electron-donating groups present; see: Ziegler, F. E.; Fowler, K. W. J. Org. Chem. 1976, 41, 1564. For a list of other benzaldehyde-related ortho directing groups see ref 8.
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15844419574
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note
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Since the dimethylamide was ultimately desired, the metalation-carboxylation of 4-chlorobenzaldehyde was carried out with dimethylcarbamoyl chloride. The dimethylcarbamide derivative was obtained cleanly; however, upon subjecting the material to the coupling reaction the amide was easily hydrolyzed in situ to provide only 7b. (Equation Presented)
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37
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(d) Mathre, D. J.; Jones, T. K.; Xavier, L. C.; Blacklock, T. J.; Reamer, R. A.; Mohan, J. J.; Turner Jones, E. T.; Hoogsteen, K.; Baum, M. W.; Grabowski, E. J. J. J. Org. Chem. 1991, 56, 751.
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0000627594
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(f) For the application of B-chlorodiisopinocampheylborane to these systems see ref 5
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(e) Mathre, D. J.; Thompson, A. S.; Douglas, A. W.; Hoogsten, K.; Carroll, J. D.; Corley, E. G.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 2880. (f) For the application of B-chlorodiisopinocampheylborane to these systems see ref 5.
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44
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15844376511
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note
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The alkylation of the hydroxy ester 3b gave the crystalline product i. However, a major byproduct in the alkylation was the lactone ii (38%) formed by intramolecular esterification. Although the mixture of i and ii could be converted to 13, purification and isolation of the reaction intermediate was compromised. (Equation Presented)
-
-
-
-
45
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0029164255
-
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For the preparation of the ethene bridge via the Wittig olefination, see: Lau, C. K.; Dufresne, C.; Gareau, Y ; Zamboni, R.; Labelle, M.; Young, R. N ; Metters, K. M.; Rochette, C.; Sawyer, N.; Slipetz, D. M.; Charette, L.; Jones, T.; McAuliffe, M.; McFarlane, C.; Ford-Hutchinson, A. W. Bioorg. Med. Chem. Lett. 1995, 5, 1615.
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47
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0000633011
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Vinyl Substitutions with Organopalladium Intermediates
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Trost, B. M., Ed.; Pergamon Press: New York, Chapter 3, (c) References cited in ref 5
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(b) Heck, R. F. Vinyl Substitutions with Organopalladium Intermediates. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: New York, 1991; Vol. 4, Chapter 3, p 833. (c) References cited in ref 5.
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Heck, R.F.1
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