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Volumn 71, Issue 21, 2006, Pages 8178-8182

Fe(0)-mediated synthesis of tri- and tetra-substituted olefins from carbonyls: An environmentally friendly alternative to Cr(II)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL NITRILE; CARBONYLS; STEREOSELECTIVITY;

EID: 33750000015     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo061445u     Document Type: Article
Times cited : (29)

References (47)
  • 16
    • 24644523532 scopus 로고    scopus 로고
    • For recent examples of the application of iron derivatives in the formation of C-C bonds, see: (a) Fürstner, A.; Martin, R.; Majima, K. J. Am. Chem. Soc. 2005, 127, 12236.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 12236
    • Fürstner, A.1    Martin, R.2    Majima, K.3
  • 33
  • 34
    • 33749994643 scopus 로고    scopus 로고
    • note
    • Fe(0) powder (< 10 μm, 99.9%) was purchased from Aldrich and Alfa Aeser and stored/handled under an inert atmosphere to minimize formation of an oxide coating.
  • 37
    • 0035913734 scopus 로고    scopus 로고
    • Control experiments indicate that 23 and 25 are stable under the reaction conditions. We speculate the minor amounts of debrominated byproducts arise via double metalation of the initial Reformatsky-type adduct i to give ii. We and others have previously invoked the generation of gemdichromium intermediates: Baati, R.; Barma, D. K.; Falck, J. R.; Mioskowski, C. J. Am. Chem. Soc. 2001, 123, 9196. The greater reactivity of bromides makes this process partially competitive with the pathway in Figure 1 (Diagram presented)
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 9196
    • Baati, R.1    Barma, D.K.2    Falck, J.R.3    Mioskowski, C.4
  • 39
    • 33750002189 scopus 로고    scopus 로고
    • note
    • In sharp contrast, reactions of methyl tribromoacetate with ketones afforded complex product mixtures. This may reflect its greater steric profile and/or the proclivity of the more reactive bromides toward undesired side reactions.
  • 42
    • 33749992024 scopus 로고    scopus 로고
    • note
    • Considering standard reduction potentials of Fe(II)/Fe (-0.45 V), Fe(III)/Fe (-0.04 V), and Fe(III)/Fe(II) (+0.77 V) compared to Cr(III)/Cr(II) (-0.41 V), we postulate the formation of Fe(II) salts in the tandem Reformatsky elimination reaction.
  • 43
    • 33750031932 scopus 로고    scopus 로고
    • note
    • 2O, 0 °C, 20 min) of the ester and 2D nOe analysis of the resultant primary alcohols; comparable treatment of 42 gave an unstable product, so its stereochemistry could not be established.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.