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For the isolation and biological activities of (-)-agelastatin A: (a) D'Ambrosio, M.; Guerriero, A.; Debitus, C.; Ribes, O.; Pusset, J.; Leroy, S.; Pietra, F. J. Chem. Soc., Chem. Commun. 1993, 1305.
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For the isolation and biological activities of (-)-agelastatin A: (a) D'Ambrosio, M.; Guerriero, A.; Debitus, C.; Ribes, O.; Pusset, J.; Leroy, S.; Pietra, F. J. Chem. Soc., Chem. Commun. 1993, 1305.
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(a) Hale, K. J.; Domostoj, M. M.; Tocher, D. A.; Irving, E.; Scheinmann, F. Org. Lett. 2003, 5, 2927.
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22
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34547943393
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Benzoate 11 was readily prepared from commercially available L-arabitol in 80% yield over two steps through acetonidation followed by protection of the resultant primary alcohol as benzoate. See, Bukhari, M. S.; Foster, A. B.; Lehmann, J.; Webber, J. M.; Westwood, J. H. J. Chem. Soc. 1963, 2291.
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Benzoate 11 was readily prepared from commercially available L-arabitol in 80% yield over two steps through acetonidation followed by protection of the resultant primary alcohol as benzoate. See, Bukhari, M. S.; Foster, A. B.; Lehmann, J.; Webber, J. M.; Westwood, J. H. J. Chem. Soc. 1963, 2291.
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37049087800
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This dehydration condition was first reported as a synthetic method for the preparation of isonitrile from formamide. See: Ichikawa, Y. J. Chem. Soc, Perkin Trans. 1 1992, 2135
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This dehydration condition was first reported as a synthetic method for the preparation of isonitrile from formamide. See: Ichikawa, Y. J. Chem. Soc., Perkin Trans. 1 1992, 2135.
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29
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33748734782
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Addition of tributyltin alkoxide enhanced the yields of this in situ transformation of isocyanate into the corresponding carbamate. See: (a) Ichikawa, Y, Osada, M, Ohtani, I, Isobe, M. J. Chem. Soc, Perkin Trans. 1 1997, 1449
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Addition of tributyltin alkoxide enhanced the yields of this in situ transformation of isocyanate into the corresponding carbamate. See: (a) Ichikawa, Y.; Osada, M.; Ohtani, I.; Isobe, M. J. Chem. Soc., Perkin Trans. 1 1997, 1449.
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32
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34547939612
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Our initial route focused on exploiting the fully protected 1,6-diene i as a substrate for RCM, because oxazolidinone ring was expected to induce turn-structure on the diene to facilitate the ring- closure process; in fact, cyclopentene ii was obtained in good yields. Unfortunately, we encountered difficulty associated with the manipulation of the carbamate group in ii, which revised our protecting group strategy. As a result, 8 was chosen as a substrate for RCM. Equation presented
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Our initial route focused on exploiting the fully protected 1,6-diene i as a substrate for RCM, because oxazolidinone ring was expected to induce turn-structure on the diene to facilitate the ring- closure process; in fact, cyclopentene ii was obtained in good yields. Unfortunately, we encountered difficulty associated with the manipulation of the carbamate group in ii, which revised our protecting group strategy. As a result, 8 was chosen as a substrate for RCM. Equation presented.
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33
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(a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 2039.
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France, M.B.2
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Grubbs, R.H.4
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35
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41649120463
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Similar strategy using bromopyrrole was noted in the previous synthesis of Hale, which was rationalized and modified in our route. Hale, K. J.; Domostoj, M. M.; El-Tanami, M.; Campbell, F. C.; Mason, C. K. Total Synthesis and Mechanism of Action Studies on the Antitumor Alkaloid, (-)-agelastatin A. In Strategies and Tactics in Organic Synthesis; Harmata, M., Ed.; Elsevier: 2005; pp 352-394. See also ref 10b and Supporting Information.
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Similar strategy using bromopyrrole was noted in the previous synthesis of Hale, which was rationalized and modified in our route. Hale, K. J.; Domostoj, M. M.; El-Tanami, M.; Campbell, F. C.; Mason, C. K. Total Synthesis and Mechanism of Action Studies on the Antitumor Alkaloid, (-)-agelastatin A. In Strategies and Tactics in Organic Synthesis; Harmata, M., Ed.; Elsevier: 2005; pp 352-394. See also ref 10b and Supporting Information.
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0000295212
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(a) Frigerio, M.; Santagostino, M.; Sputore, S.; Palmisano, G. J. Org. Chem. 1995, 60, 7272.
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Frigerio, M.1
Santagostino, M.2
Sputore, S.3
Palmisano, G.4
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40
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34547954682
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Commercially available methyl isocyanate was dissolved in THF and then used as a THF-solution, which was titrated by the reaction with excess benzylamine and isolation of the produced methyl benzyl urea. We thank Prof. Weinreb, Dr. Stien, and Prof. Davis for informing us of the source of methyl isocyanate see ref 8a and 11
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Commercially available methyl isocyanate was dissolved in THF and then used as a THF-solution, which was titrated by the reaction with excess benzylamine and isolation of the produced methyl benzyl urea. We thank Prof. Weinreb, Dr. Stien, and Prof. Davis for informing us of the source of methyl isocyanate (see ref 8a and 11).
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