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. Author manuscript; available in PMC: 2017 Sep 7.
Published in final edited form as: J Am Chem Soc. 2016 Aug 24;138(35):11176–11184. doi: 10.1021/jacs.6b04915

Scheme 5. Proposed biogenesis of glandicoline A (4) and B (5).

Scheme 5

The nitrone intermediate 7 described by Ries et al. and in this work is likely a key priming step for the rearrangement to 6. Compound 5 is not observed in P. chrysogenum or P. oxalicum F30 but is a known natural product. One possible route to 5 is through dehydration of the hydroxylamine intermediate 15 followed by hydroxylation and rearrangement. Enzymatic processing of 5 to 4 must also be considered.