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For recent applications see: (c) Semmelhack, M. F.; Campagna, S. R.; Federle, M. J.; Bassler, B. L. Org. Lett. 2005, 7, 569.
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4 mediated alkyne oxidation, For a recent review, see: e
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4 mediated alkyne oxidation).
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Plietker, B.1
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2/DMSO mediated alkyne double oxidation, see: Yusybov, M. S.-O.; Filimonov, V. D. Synthesis 1991, 131.
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2/DMSO mediated alkyne double oxidation, see: Yusybov, M. S.-O.; Filimonov, V. D. Synthesis 1991, 131.
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74
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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
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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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75
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0034822714
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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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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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76
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Also see: b
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Also see: (b) Murray, R. W.; Singh, M.; Marron, T. G.; Pfeifer, L. A.; Roush, W. R. Org. Synth. 1997, 74, 91.
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Murray, R.W.1
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Pfeifer, L.A.4
Roush, W.R.5
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77
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1H NMR spectra resulting from the oxidation of ynamide 9 under these conditions suggests this course of action.
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1H NMR spectra resulting from the oxidation of ynamide 9 under these conditions suggests this course of action.
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78
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For an excellent review on the chemistry of vicinal tricarbonyls and related systems, see
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For an excellent review on the chemistry of vicinal tricarbonyls and related systems, see: Wasserman, H. H.; Parr, J. Acc. Chem. Res. 2004, 37, 687.
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79
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1H NMR.
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1H NMR.
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80
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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.
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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.
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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].
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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].
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82
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For a lead reference on ruthenium mediated alkene oxidation see: a
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For a lead reference on ruthenium mediated alkene oxidation see: (a) Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
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For a recent application see: b
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For a recent application see: (b) Neisius, N. M.; Plietker, B. J. Org. Chem. 2008, 73, 3218.
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84
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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.
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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.
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