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note
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1,3 strain with the carbonyl group. In fumiquinazoline A (1), the methyl group at C-3, which is trans to R, is equatorial-like. Therefore, there is a 81° torsion angle between the axial-like H-3 and N-H (PCMODEL 7.5), which is consistent with the observed 0.3-Hz coupling constant. In fumiquinazoline B (2), the methyl group, which is cis to R, is axial-like. Therefore there is a 46° torsion angle between the equatorial H-3 and N-H, which is consistent with the observed 4.9-Hz coupling constant. The coupling constant reported for 5 in ref 1 is 0.3 Hz, which indicates that the substituents are trans not cis and that this compound actually has structure 6 (50b). The coupling constant reported for 6 in ref 1 is 4.2 Hz, which indicates that the substituents are cis not trans and that this compound actually has structure 5 (50a).
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34
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12244279020
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note
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2 or DDQ was unsuccessful.
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12244311188
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note
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3CN without acetic acid for 2 h yields 54b in 33% yield with 15% of the C-14 epimer, 7% of 60, and 4% of the cyclic ether from the C-14 epimer.
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42
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12244257517
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note
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22 Presumably the selective formation of 59 from 54b is a result of axial-like addition of methanol to the intermediate cation.
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