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Volumn , Issue 23, 2010, Pages 4460-4467

Dehydrogenative functionalization of C(sp3)-H bonds adjacent to a heteroatom mediated by oxoammonium salts

Author keywords

C H activation; Cross coupling; Dehydrogenation; Iron

Indexed keywords


EID: 77955366794     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.201000548     Document Type: Article
Times cited : (165)

References (80)
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    • 3)-H bond iunctionalizations, see: a) Y. Zhang, C.J. Li, Eur. J. Org. Chem. 2007, 4654-4657;
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    • Oxoammonium- And nitroxide-catalyzed oxidations of alcohols
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    • For a comprehensive review on oxoammonium chemistry, see: a) J. M. Bobbitt, C. Brückner, N. Merbouh, "Oxoammonium- and Nitroxide-Catalyzed Oxidations of Alcohols" in Organic Reactivity (Ed.: S. E. Denmark), Wiley, New York, 2009, vol. 74, pp 103-424; for some recent examples, see:
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    • and references cited. therein; for oxidations to carboxylic acids, see
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    • See, for example, alcohol rearrangements: a
    • See, for example, alcohol rearrangements: a) M. Shibuya, M. Tomizawa, Y. Iwabuchi, J. Org. Chem. 2008, 73, 4750-4752;
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    • for a related suggested mechanism, involving prior complexation of the substrate with the oxoammonium salt, see: b
    • for a related suggested mechanism, involving prior complexation of the substrate with the oxoammonium salt, see: b) F. Acunzo, P. Baiocco, M. Fabbrini, C. Galii, P. Gentili, Eur. J. Org. Chem. 2002, 4195-4201.
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    • [8a]
    • [8a]
  • 58
    • 77955387771 scopus 로고    scopus 로고
    • [4a]), desired coupling product 3a was only formed in small amounts (10-17%), and 4 was the major isolated product. (50-55%)
    • [4a]), desired coupling product 3a was only formed in small amounts (10-17%), and 4 was the major isolated product. (50-55%).
  • 65
    • 77955409302 scopus 로고    scopus 로고
    • +-mediated reaction between 1a and 2a, 3a was still formed but in a moderate 40 % yield. This result is also consistent with the proposed, ionic mechanism, as phenols can also react with TEMPO salts. However, a radical pathway cannot be completely ruled out on the basis of these observations
    • +-mediated reaction between 1a and 2a, 3a was still formed but in a moderate 40 % yield. This result is also consistent with the proposed, ionic mechanism, as phenols can also react with TEMPO salts. However, a radical pathway cannot be completely ruled out on the basis of these observations.
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    • Highly unstable TEMPOH was partially oxidized to TEMPO during manipulation of the GC-MS samples in air
    • Highly unstable TEMPOH was partially oxidized to TEMPO during manipulation of the GC-MS samples in air.
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    • 2 (Table 1, Entry 16)
    • 2 (Table 1, Entry 16).
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    • The use of other strong organic acids such as TfOH or AcOIi led to undesired products and/or large amounts of isochromanone (4)
    • The use of other strong organic acids such as TfOH or AcOIi led to undesired products and/or large amounts of isochromanone (4).
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    • This metal-free reaction was not efficient for tetrahydroisoquinolines, which were not tolerated (lg) or led to complex mixtures (1J, 19% 3r after 48 h)
    • This metal-free reaction was not efficient for tetrahydroisoquinolines, which were not tolerated (lg) or led to complex mixtures (1J, 19% 3r after 48 h).
  • 72
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    • 1H NMR spectroscopy studies, see the Supporting Information
    • 1H NMR spectroscopy studies, see the Supporting Information


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.