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Volumn 73, Issue 22, 2008, Pages 8780-8784

Synthesis of α-keto-imides via oxidation of ynamides

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; AMINES; CHEMICAL REACTIONS; OLEFINS; OXIDATION; RUTHENIUM ALLOYS; RUTHENIUM COMPOUNDS; SILANES;

EID: 56449100050     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8015067     Document Type: Article
Times cited : (91)

References (84)
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    • (d) For a special issue dedicated to the chemistry of ynamides, see: Tetrahedron-Symposium-In-Print: "Chemistry of Electron-Deficient Ynamines and Ynamides." Tetrahedron 2006, 62, Issue No. 16.
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    • We attempted these conditions because of an intriguing observation: During the preparation of ynamide 13, an extended reaction time of 24 h (rather than 4 h) employing Stahl's amidation conditions [see ref 2b] with stoichiometric CuCl2 in DMSO under O2 led to the isolation of ∼7% yield of a mixture of ynamide 13 and α-keto-imide 19 with a ratio of 1.4:1 [see Table 2 for structures
    • 2 led to the isolation of ∼7% yield of a mixture of ynamide 13 and α-keto-imide 19 with a ratio of 1.4:1 [see Table 2 for structures].
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    • DMDO/acetone solutions were prepared following the procedure reported in: (a) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174.
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    • 1H NMR spectra resulting from the oxidation of ynamide 9 under these conditions suggests this course of action.
    • 1H NMR spectra resulting from the oxidation of ynamide 9 under these conditions suggests this course of action.
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    • 1H NMR.
    • 1H NMR.
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    • 3] that is susceptible to undergo Wolff rearrangement and subsequent transformations through the resulting silyl ketene intermediate. Further studies are underway.
    • 3] that is susceptible to undergo Wolff rearrangement and subsequent transformations through the resulting silyl ketene intermediate. Further studies are underway.
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    • We observed loss of the N-sulfonyl group during DMDO oxidations of N-sulfonyl-substituted ynamides such as 31 [also observed for 11 shown in Table 2].
    • We observed loss of the N-sulfonyl group during DMDO oxidations of N-sulfonyl-substituted ynamides such as 31 [also observed for 11 shown in Table 2].
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    • For a recent application see: b
    • For a recent application see: (b) Neisius, N. M.; Plietker, B. J. Org. Chem. 2008, 73, 3218.
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    • 2O (0.2 M), comparing the integration values corresponding to the proton peaks belonging to the remaining thioanisole and the resulting methyl phenyl sulfoxide.
    • 2O (0.2 M), comparing the integration values corresponding to the proton peaks belonging to the remaining thioanisole and the resulting methyl phenyl sulfoxide.


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