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Volumn 127, Issue 36, 2005, Pages 12513-12515

Deoxygenation of alcohols employing water as the hydrogen atom source

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN; WATER;

EID: 24744461879     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052185l     Document Type: Article
Times cited : (200)

References (44)
  • 3
  • 16
    • 0000829322 scopus 로고
    • For lead references on stoichiometric tin hydride substitutes, see: for silanes (a) Chatgilialoglu, C. Acc. Chem. Res. 1992, 25, 188.
    • (1992) Acc. Chem. Res. , vol.25 , pp. 188
    • Chatgilialoglu, C.1
  • 22
    • 24744441804 scopus 로고    scopus 로고
    • note
    • Reduction of 5, as described in ref 1. provided 8 in 78% yield.
  • 23
    • 24744452717 scopus 로고    scopus 로고
    • note
    • The reduction product was isolated in 62% yield versus 90% in reactions containing tributyltin hydride (ref 3). Further evidence for slow reduction under tin-free conditions was the isolation of products from radical recombination (9%) and disproportionation (12%).
  • 26
    • 24744463759 scopus 로고    scopus 로고
    • note
    • The full details of these sludies will be disclosed at a later date.
  • 27
    • 24744436078 scopus 로고    scopus 로고
    • note
    • 13C NMR analysis, and neither workup or flask transfer was necessary for product purification, the possibility that a C-H bond in 5 or 8 was providing the H-atom in these reactions was discounted.
  • 28
    • 24744438335 scopus 로고    scopus 로고
    • note
    • For full details of these studies, please refer to the Supporting Information.
  • 31
  • 33
    • 0036250217 scopus 로고    scopus 로고
    • 3-air mixtures. Substantial kinetic and/or mechanistic differences between these methods and the reductions reported herein are likely operating. For more detail on aqueous radical reactions, see: Yorimitsu, H.; Shinokubo, H.; Oshima. K. Synlett 2002, 5, 674-686.
    • (2002) Synlett , vol.5 , pp. 674-686
    • Yorimitsu, H.1    Shinokubo, H.2    Oshima, K.3
  • 36
    • 0000915956 scopus 로고
    • Many of the examples in Table 2 required only substoichiometric oxygen, implying that a chain mechanism is operating. However, the uncontrolled entry of additional oxygen through rubber septa cannol be excluded at this time. Furthermore, the slow introduclion of air was critical to achieving high yields in these reactions, as observed in other trialkylborane-mediated free-radical processes. See, for example: (a) Brown, H. C.; Kabalka, G. W. J. Am. Chem. Soc. 1970, 92, 714-716.
    • (1970) J. Am. Chem. Soc. , vol.92 , pp. 714-716
    • Brown, H.C.1    Kabalka, G.W.2
  • 39
    • 0004181436 scopus 로고
    • Academic Press: New York
    • The further observation that the reaction of xanthale 11 was completely inhibited by galvinoxyl suggests that the initial generation of alkyl radicals from trialkylboranes (Onak. T. Organoborane Chemistry; Academic Press: New York, 1975; p 360) is critical to the mechanism. The isolation of 24 (R′ = Bu) in 97% yield also supports the proposed mechanism.
    • (1975) Organoborane Chemistry , pp. 360
    • Onak, T.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.