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Volumn 40, Issue 6, 2011, Pages 555-557

Oxidative C-H/C-H coupling of azine and indole/pyrrole nuclei: Palladium catalysis and synthesis of eudistomin U

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EID: 79956346739     PISSN: 03667022     EISSN: 13480715     Source Type: Journal    
DOI: 10.1246/cl.2011.555     Document Type: Review
Times cited : (113)

References (79)
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    • During the preparation of this manuscript, a paper dealing with the same transformation has been reported by Li and co-workers
    • During the preparation of this manuscript, a paper dealing with the same transformation has been reported by Li and co-workers. X. Gong, G. Song, H. Zhang, X. Li, Org. Lett. 2011, 13, 1766.
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    • For Pd-catalyzed C-H/C-X cross-coupling of azine N-oxides with haloarenes pioneered by Fagnou, see: a
    • For Pd-catalyzed C-H/C-X cross-coupling of azine N-oxides with haloarenes pioneered by Fagnou, see: a) L.-C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 2005, 127, 18020.
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    • See the Supporting Information for further details
    • See the Supporting Information for further details.
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    • We assume that 2, 6-lutidine help stabilizing Pd species as a ligand
    • We assume that 2, 6-lutidine help stabilizing Pd species as a ligand.
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    • 3 is essential presumably as an oxidant for Pd 0-to-Pd II process see the Supporting Information for details. For other representative examples using Ag I oxidants in Pd-catalyzed oxidative C-H functionalization, see: a, For a recent review describing important roles of external oxidants in Pd II - catalyzed C-H functionalization, see
    • 3 is essential presumably as an oxidant for Pd (0)-to-Pd (II) process (see the Supporting Information for details). For other representative examples using Ag (I) oxidants in Pd-catalyzed oxidative C-H functionalization, see: a) X. Chen, C. E. Goodhue, J.-Q. Yu, J. Am. Chem. Soc. 2006, 128, 12634. For a recent review describing important roles of external oxidants in Pd (II) - catalyzed C-H functionalization, see:
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    • This phenomenon was observed only for pyrrole derivatives. In the case of indoles, the corresponding product could not be obtained using any substrates devoid of protecting groups. The regioselectivity observed in the pyrrole reactions might be engendered by the steric bulk of the protecting groups. For a review, see:, Further studies are in progress to elucidate the controlling elements in regioselectivity
    • This phenomenon was observed only for pyrrole derivatives. In the case of indoles, the corresponding product could not be obtained using any substrates devoid of protecting groups. The regioselectivity observed in the pyrrole reactions might be engendered by the steric bulk of the protecting groups. For a review, see: L. Joucla, L. Djakovitch, Adv. Synth. Catal. 2009, 351, 673. Further studies are in progress to elucidate the controlling elements in regioselectivity.
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    • yield of the coupling product was ca. 50% in the presence of 2, 6-lutidine as an additive. The yield improved to 63% without 2, 6-lutidine, and is of slightly higher yield 70% in the presence of acetic acid
    • The yield of the coupling product was ca. 50% in the presence of 2, 6-lutidine as an additive. The yield improved to 63% without 2, 6-lutidine, and is of slightly higher yield (70%) in the presence of acetic acid.
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    • Supporting Information is available electronically on the CSJ-Journal Web site
    • Supporting Information is available electronically on the CSJ-Journal Web site, http://www.csj.jp/journals/chem-lett/index.html.


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