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Volumn 130, Issue 8, 2009, Pages 702-707

Asymmetric oxidative α-fluorination of 2-alkylphenylacetaldehydes with AgHF2 and ruthenium/PNNP catalysts

Author keywords

Asymmetric fluorination; Fluoroaldehydes; PNNP ligands; Ruthenium; Silver bifluoride

Indexed keywords


EID: 67650587755     PISSN: 00221139     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jfluchem.2009.05.008     Document Type: Article
Times cited : (24)

References (70)
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    • Selected papers
    • Selected papers:
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    • Epoxide to carbonyl rearrangements are well-documented in the literature
    • Epoxide to carbonyl rearrangements are well-documented in the literature.
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    • The first example involving Brønsted acid catalysis see:
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    • The oxidative cleavage of 2-phenylpropionaldehyde to acetophenone under aerobic conditions and in the presence of H+ or of Lewis acidic metal ions (Cu(II), Ce(III), V(IV)) has been reported:
    • The oxidative cleavage of 2-phenylpropionaldehyde to acetophenone under aerobic conditions and in the presence of H+ or of Lewis acidic metal ions (Cu(II), Ce(III), V(IV)) has been reported:. Tokunaga M., Aoyama H., Shirogane Y., Obora Y., and Tsuji Y. Catal. Today 117 (2006) 138-140
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    • note
    • Enantioselectivities of up to 44% ee were obtained in some preliminary experiments, however, these higher values were not reproducible.
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    • For a review on carbocations substituted with electron-withdrawing groups, see:
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    • For a review on α-carbonyl cations, see:. Creary X. (Ed), Jai Press Ltd.
    • For a review on α-carbonyl cations, see:. Creary X., Hopkinson A.C., and Lee-Ruff E. In: Creary X. (Ed). Advances in Carbocation Chemistry vol. 1 (1989), Jai Press Ltd. 45-92
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    • Alternatively, an oxidation mechanism by hydride abstraction might be considered. During our investigations of a Ru/PNNP complex containing a coordinated β-keto ester enolate, we found that Ag+ is able to formally abstract a hydride from the ligand producing an α-alkenyl-β-keto ester [29b]. The removal of a hydride from the aldehyde by silver(I) would directly lead to an α-carbonyl cation. However, we do not have conclusive evidence for such a mechanism.
    • Alternatively, an oxidation mechanism by hydride abstraction might be considered. During our investigations of a Ru/PNNP complex containing a coordinated β-keto ester enolate, we found that Ag+ is able to formally abstract a hydride from the ligand producing an α-alkenyl-β-keto ester [29b]. The removal of a hydride from the aldehyde by silver(I) would directly lead to an α-carbonyl cation. However, we do not have conclusive evidence for such a mechanism.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.