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Attempts at developing the Pd(0)-catalyzed reaction of allylic esters with silyl enol ethers derived from simple ketones, as an extension of the established reactions with stabilized C-nucleophiles, have only met with modest success. In the examples reported to date, the more reactive carbonates (rather than acetates) have been employed and some of these reactions seem to work efficiently only as intramolecular processes: (a) Tsuji, J.; Minami, I.; Shimizu, I. Chemistry Lett. 1983, 1325.
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0344639705
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Note that the opposite effect has been observed for the substrates in which the syn-mechanism is precluded by a steric bias so that the anti-mechanism (5) becomes the only possible pathway.11
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49
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0345501841
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note
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22
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68
-
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0345501839
-
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note
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2 at room temperature with 2-5 mol % of the catalyst and a slight excess (1,1 equiv) of the nucleophile. The reaction times and yields are given in Tables 1-6. All yields refer to "isolated" yields rather than "GC yields".
-
-
-
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69
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0028348463
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For a similar catalytic effect of Ce(IV) and/or Ce(III) on the transformation of allylic acetates or alcohols into the corresponding ethers on reaction with alcohols, see: (a) Iranpoor, N.; Mothaghineghad, E. Tetrahedron 1994, 50, 1859 and 7299.
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Iranpoor, N.1
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0031543126
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2 as catalyst: Sakamaki, H.; Kameda, N.; Iwadare, T.; Ichinohe, Y. Bull. Chem. Soc. Jpn 1995, 68, 3491.
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Uzarewicz, A.1
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0040553332
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2 as catalyst: Sakamaki, H.; Kameda, N.; Iwadare, T.; Ichinohe, Y. Bull. Chem. Soc. Jpn 1995, 68, 3491.
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0001436414
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See also refs 8e,f
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Enolates of β-dicarbonyls are known to form relatively stable chelate complexes with Mo(II): Brower, D. C.; Winston, P. B.; Tonker, T. L.; Templeton, J. L. Inorg. Chem. 1986, 25, 2883. See also refs 8e,f.
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Brower, D.C.1
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0345501835
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3SiCl.
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74
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Hayaahi, T.; Yamamoto, A.; Hagihara, T. J. J. Org. Chem. 1986, 51, 723.
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(a) Åkermark, B.; Hansson, S.; Krakenberger, B.; Vitagliano, A.; Zetterberg, K. Organometallics 1984, 3, 679.
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(b) Åkermark, B.; Krakenberger, B.; Hansson, S.; Vitagliano, A. Organometallics 1987, 6, 620.
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78
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0344639684
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note
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4a,e this is not the case with our Mo(II) catalysts, as revealed by analysis of the reaction mixtures at ∼50% conversion of 26 and 27 with MeOH and with 32. Hence, our results are not distorted by isomerization prior to the substitution reaction.
-
-
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79
-
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0344208116
-
-
note
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D +36.9; ≥ 99% ee). However, this result could not be reproduced later. Painstaking analysis revealed that one batch of the starting ennatiomerically pure alcohol, used for the preparation of acetate (R)-(+)-23, was contaminated by ca. 5% of diisopropyl tartrate, originating from the Sharpless epoxidation (in kinetic resolution mode). Apparently, the tartrate, still present in the Mo(II)-catalyzed reaction, was the source of this error.
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81
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For other examples of Lewis-acidic transition metal complexes, see, e.g.: Hollis, K.; Odenkirk, W.; Robinson, N. P.; Whelan, J.; Bosnich, B. Tetrahedron 1993, 49, 5415.
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For a recent, detailed discussion of the competing ionic and SET mechanism in the Mukaiyama-Michael reaction, and its dependence on the Lewis acid employed and the steric bulk of the reaction partners, see: Otera, J.; Fujita, Y.; Sakuta, N.; Fujita, M.; Fukuzumi, S. J. Org. Chem. 1996, 61, 2951.
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For the Mo-and W-template-controlled allylic substitution, see refs 8-13. For the formation of a stable π-allyl complex on reaction of allyl chloride with 11a.b, see: Hull, C. G.; Stiddard, M. H. B. J. Organomet. Chem. 1967, 9, 519.
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For catalytic activity of 8 in the Friedel-Crafts-type allylation of electron rich aromatics, and in the carbonyl ene-type cyclizations, see: (a) Malkov, A. V.; Davis, S. L.; Baxendale, I. B.; Mitchell, W. L.; Kočovský, P. J. Org. Chem. 1999, 64, 2751-2764.
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Allylic acetates references, as follows: 16: (a) Lessard, J.; Tan, P. V. M.; Martino, R.; Sanders, J. K. Can. J. Chem. 1977, 55, 1015. 17:
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