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6
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33645450011
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For a modified approach and the synthesis of the non-natural enantiomer (+)- 1, see:
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P. S. Baran N. Z. Burns J. Am. Chem. Soc. 2006 128 3908
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13
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0037067104
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The use of in situ generated ylide invariably led to lower yields and various degree of epimerization; the procedure described in the following publication was used to prepare the ylide:
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A. Endo A. Yanagisawa M. Abe S. Tohma T. Kan T. Fukuyama J. Am. Chem. Soc. 2002 124 6552
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22
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20544450502
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A. de Meijere and. F. Diederich. Wiley-VCH. Weinheim, 2nd edn. p. 217. Other protocols afforded appreciable amounts of the corresponding saturated ketone rather than the desired enone. Under the optimized conditions, however, the enone: ketone ratio was invariably greater than 10: 1. For a discussion see:
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S. Bräse and A. de Meijere, in Metal-Catalyzed Cross-Coupling Reactions, ed., A. de Meijere, and, F. Diederich,, Wiley-VCH, Weinheim, 2nd edn, 2004, vol. 1, p. 217
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Bräse, S.1
De Meijere In, A.2
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24
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0004219714
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M. Schlosser, Wiley, Chichester, 2nd edn, p. 669
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B. H. Lipshutz, in Organometallics in Synthesis. A Manual, ed., M. Schlosser,, Wiley, Chichester, 2nd edn, 2002, p. 669
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Lipshutz In, B.H.1
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26
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0001026255
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2 at -78°C, a ∼1: 1 mixture of the two possible enol triflates is formed. This result suggests that the selective formation of compound 23 under the chosen conditions is mostly thermodynamic in origin
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M. E. Garst J. N. Bonfiglio D. A. Grudoski J. Marks J. Org. Chem. 1980 45 2307
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30
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33845376366
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The rather poor yield in this step is ascribed to the low stability of the pyrone entities of 27 and 28 in refluxing toluene
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W. J. Scott J. K. Stille J. Am. Chem. Soc. 1986 108 3033
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36
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A. Fürstner C. Nevado M. Tremblay C. Chevrier F. Teplý C. Aïssa M. Waser Angew. Chem., Int. Ed. 2006 45 5837
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37
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A. Fürstner L. C. Bouchez J.-A. Funel V. Liepins F.-H. Porée R. Gilmour F. Beaufils D. Laurich M. Tamiya Angew. Chem., Int. Ed. 2007 46 9265
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38
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45549096617
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10.1039/b805299a. (accompanying paper). Attempts to reproduce the end game did afford the desired product but the yields were much lower than those reported in the literature, despite considerable experimentation. However, the small amounts of product allowed us to confirm the absolute configuration assigned to (-)-. 1 by comparison with an authentic sample. The two known asymmetric syntheses of the key intermediate. 25 compare as follows: . . . . . . . . . . . . . .
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A. Fürstner J.-A. Funel M. Tremblay L. C. Bouchez C. Nevado J. Ackerstaff C. C. Stimson Chem. Commun. 2008 10.1039/b805299a
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Stimson, C.C.7
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