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Volumn 5, Issue 3, 2010, Pages 486-489

Manganese-catalyzed direct oxidation of methyl ethers to ketones

Author keywords

C H activation; Ketones; Manganese; Methyl ethers; Oxidation

Indexed keywords

ALKYL ETHERS; C-H ACTIVATION; CARBONYL COMPOUNDS; CHEMICAL EQUATIONS; CHEMOSELECTIVE; DIRECT OXIDATION; ELECTRON-DEFICIENT; METHYL ETHERS; PROTECTIVE GROUP; REACTION CONDITIONS; TERPYRIDINES;

EID: 77749292818     PISSN: 18614728     EISSN: 1861471X     Source Type: Journal    
DOI: 10.1002/asia.200900420     Document Type: Article
Times cited : (13)

References (51)
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    • For representative applications of methyl ethers as a synthetic intermediate in total syntheses
    • For representative applications of methyl ethers as a synthetic intermediate in total syntheses, see:a) E. J. Corey, B. Hong, J. Am. Chem. Soc. 1994, 116, 3149.
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    • For recent reviews of direct C-H oxidation
    • For recent reviews of direct C-H oxidation, see:a) T. Naota, H. Takaya, S.-I. Murahashi, Chem. Rev. 1998, 98, 2599.
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    • (Eds.: K. I. Goldberg, A. S. Goldman), American Chemical Society, Washington, DC
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    • (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, Chap. 2-6, and references therein
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    • Murahashi, S.1    Oda, Y.2    Naota, T.3
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    • For examples of direct methyl ether oxidation
    • For examples of direct methyl ether oxidation, see: a) R. D. Bach, T. H. Taaffee, J. W. Holubka, J. Org. Chem. 1980, 45, 3439.
    • (1980) J. Org. Chem. , vol.45 , pp. 3439
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  • 33
    • 33646100085 scopus 로고    scopus 로고
    • For recent reports on Mn-catalyzed epoxidation under similar systems
    • For recent reports on Mn-catalyzed epoxidation under similar systems, see:a) A. Murphy, S. P. Stack, J. Mol. Catal. A 2006, 251, 78.
    • (2006) J. Mol. Catal. A , vol.251 , pp. 78
    • Murphy, A.1    Stack, S.P.2
  • 40
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    • 3CN without the manganese reagent only led to recovery of 1a (99%)
    • 3CN without the manganese reagent only led to recovery of 1a (99%).
  • 44
    • 77749246319 scopus 로고    scopus 로고
    • Over-oxidation took place to produce cyclodocecane-1, 5-dione as the by-product (<5% yield)
    • Over-oxidation took place to produce cyclodocecane-1, 5-dione as the by-product (<5% yield).
  • 49
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    • See the Experimental Section
    • See the Experimental Section.
  • 50
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    • As a separate experiment, we found that alcohol 5 was also oxidized to ketone 2a under these conditions in high yield, supporting the intermediacy of 5 via 4 in the reactions of entries 2-4
    • As a separate experiment, we found that alcohol 5 was also oxidized to ketone 2a under these conditions in high yield, supporting the intermediacy of 5 via 4 in the reactions of entries 2-4.
  • 51
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    • The oxidation of octyl methyl ether under the standard reaction conditions afforded octanoic acid in 47% NMR yield. This result shows that the present Mn-catalyzed oxidation of primary methyl ethers produces the corresponding carboxylic acids as a product
    • The oxidation of octyl methyl ether under the standard reaction conditions afforded octanoic acid in 47% NMR yield. This result shows that the present Mn-catalyzed oxidation of primary methyl ethers produces the corresponding carboxylic acids as a product.


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