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The feasibility of attaining stereocontrol by rotation around the σ bonds flanking an olefinic linkage has been previously demonstrated by us in a tricyclic precursor to taxusin: (a) Paquette, L. A.; Zhao, M. J. Am. Chem. Soc. 1993, 115, 354. (b) Paquette, L. A.; Zhao, M. J. Am. Chem. Soc. 1998, 120, 5203.
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The feasibility of attaining stereocontrol by rotation around the σ bonds flanking an olefinic linkage has been previously demonstrated by us in a tricyclic precursor to taxusin: (a) Paquette, L. A.; Zhao, M. J. Am. Chem. Soc. 1993, 115, 354. (b) Paquette, L. A.; Zhao, M. J. Am. Chem. Soc. 1998, 120, 5203.
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note
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4 in the absence of Cul and HMPA afforded 26 in only 11% yield.
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0346315727
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note
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2, or HMPA, the allylic mercury intermediate was the only product isolated. The generation of this species appears to be rapid in all media. The ensuing step in which Hg(II) is reduced to Hg(0) is believed to be the rate-determining step. If so, the role of nonpolar benzene is to stabilize the transition state and accelerate the overall rate.
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0346315726
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Unpublished observations in this laboratory
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Yang, J. Unpublished observations in this laboratory.
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Yang, J.1
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57
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0347576697
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note
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1H NMR spectrum or a sample of natural jatrophatrione, Professor Robert Bates responded (letter dated December 15, 1995) that neither could be located at that time.
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58
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0346315725
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Footnote 15 of ref 4
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Footnote 15 of ref 4.
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