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33750468043
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It is of note that Kwon and MacMillan groups revealed their efforts to generate the [5-7-6] core by an IMDA reaction (see refs 5m and http://etd.caltech.edu/etd/available/etd-10282003-135857/).
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34
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33750484060
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note
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See Supporting Information for details.
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35
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49
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33750484745
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note
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Reduction of keto ester 35 proceeded with a good selectivity, and we believed the molecular conformation of 35 might play a major role in this outcome. Compound 35 shows a certain type of ball-shape, especially the axial methyl group at C8. which will guide the reducing agent to approach the C5 ketone from its top face at -95 °C (see its crystal structure of compound 35 listed below), leading to the formation of the desired stereochemistry at C5. The stereochemistry for the trans-relationship between the proton (a) at C5 and the protons (b) of the methyl group at C8 was confirmed by ID NOESY study of compound 36 (see Supporting Information for details).
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