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With selected examples, we try to demonstrate that complex structures of natural products can be generated with surprising spontaneity. In such cases it appears that molecular complexity might emerge with minimal (if any) enzymatic assistance, through self‐construction mechanisms. Rearrangements of linear molecules, light‐induced reactions, dimerizations and multi‐component reactions could explain the formation of secondary metabolites through the intrinsic reactivity of their precursors. A few examples, amongst the most significant, are presented, along with efficient biomimetic syntheses that strengthen the hypotheses.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
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Gravel et al. (2007) studied this question.
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