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The thermolysis study described above for the 5-α series has been separately performed on the equivalent substrate in the 5-β series (see 62), which corresponds to the guanacastepene stereochemistry. In studies with this substrate, there appears to be a preference for formation of the 13-β acetoxy product (74) over the 13-αa acetoxy product (13-epi-74). The ratio of 74 to 13-epi-74 was approximately 2.3: 1.
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The X-ray shows that, while the first carbon of the isopropyl group is, indeed, β, the geminal dimethyls are α-disposed. Therefore, in addition to confirming the stereochemical assignment described above, the X-ray also rationalizes why attack of oxidizing agents occurs primarily from the β-face of the molecule. We and others continue to investigate this matter.
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1H NMR spectra of the natural product. We are grateful to Prof. Jon Clardy and Dr. Sean F. Brady for providing detailed NMR spectra of natural guanacastepene A.
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