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Representative bis-oxazoles of this type: Muscoride A (isolation)
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This is imputable to the unfavorable positioning of the 4-COOR substituent: the 5-COOR isomer is smoothly deprotonated at the C-2 Me group (ref 24), presumably because of good resonance stabilization of the ensuing anion
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This is imputable to the unfavorable positioning of the 4-COOR substituent: the 5-COOR isomer is smoothly deprotonated at the C-2 Me group (ref 24), presumably because of good resonance stabilization of the ensuing anion.
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Conceivably, 56 could be made by Rh(II)-mediated condensation of diethyl cyanomethyl-phosphonate with ethyl diazoacetoacetate according to Hoffmann, et al. (ref 27b). However, the modest yield (18%) obtained by these authors in a similar reaction of phosphonoacetonitrile with diethyl diazomalonate discouraged us from researching this possibility
-
Conceivably, 56 could be made by Rh(II)-mediated condensation of diethyl cyanomethyl-phosphonate with ethyl diazoacetoacetate according to Hoffmann, et al. (ref 27b). However, the modest yield (18%) obtained by these authors in a similar reaction of phosphonoacetonitrile with diethyl diazomalonate discouraged us from researching this possibility.
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85026863415
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Examples appear in ref 23 as well as in
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Examples appear in ref 23 as well as in: White, J. D.; Kranemann, C. L.; Kuntiyong, P. Org. Synth. 2003, 79, 244.
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(b) For 62: Haffner, C. D.; Lenhard, J. M.; Miller, A. B.; McDougald, D. L.; Dwornik, K.; Ittoop, O. R.; Gampe, R. T., Jr.; Xu, H. E.; Blanchard, S.; Montana, V. G.; Consler, T. G.; Bledsoe, R. K.; Ayscue, A.; Croom, D. J. Med. Chem. 2004, 47, 2010.
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Comprehensive bibliography: refs 9, 27b, 31, and 37, as well as: (a) Fujita, E. Heterocycles 1984, 21, 41.
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The following patents describe the preparation of some 2-(arylsulfonyl)methyloxazole-4-carboxylic esters: JP 59108772 A 19840623 Showa (Taiho Pharmaceutical Co., Ltd.), CAN 101:171238
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However, this study also revealed that a Wadsworth-Emmons olefination mode is distinctly superior
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2.8 kcal/mol for a Ph group (Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994; p 697); approximately 1.3 kcal/mol for a 4-carbomethoxy-5-methyl-2-oxazolyl group (estimated by MM+ structural optimization of the axial and equatorial conformer of the corresponding 2-cyclohexyl derivative).
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For an excellent discussion of the vinylsulfone-allylsulfone isomerization, see: and literature cited therein. See especially pp 2331 ff
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For an excellent discussion of the vinylsulfone-allylsulfone isomerization, see: El-Awa, A.; Noshi, M. N.; Mollat du Jourdin, X.; Fuchs, P. L. Chem. Rev. 2009, 109, 2315 and literature cited therein. See especially pp 2331 ff.
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Selective formation of Z-olefins in the desulfonylation of vinylsulfones is documented; e.g.: See also ref 36a and literature cited therein
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-
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72249117935
-
-
13C signal at 85 ppm. See the spectra provided in the Supporting Information
-
13C signal at 85 ppm. See the spectra provided in the Supporting Information.
-
-
-
-
131
-
-
72249086928
-
-
6 solutions
-
6 solutions.
-
-
-
-
132
-
-
72249100529
-
-
Relevant experimental protocols are provided as Supporting Information
-
Relevant experimental protocols are provided as Supporting Information.
-
-
-
-
133
-
-
72249123336
-
-
Additional details are provided as Supporting Information
-
Additional details are provided as Supporting Information.
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