Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 27, Pages 14967-14974Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103410
Keywords
asymmetric synthesis; cycloaddition; hypervalent compounds; total synthesis; transition states
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Funding
- Agence Nationale de la Recherche [ANR-10-BLAN-0721]
- CNRS
- Conseil Regional d Aquitaine
- Ministere de lEnseignement Superieur, de la Recherche et de lInnovation
- Agence Nationale de la Recherche (ANR) [ANR-10-BLAN-0721] Funding Source: Agence Nationale de la Recherche (ANR)
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Many natural products are derived from enzymatic dearomative oxygenation of 2-alkylphenolic precursors into 6-alkyl-6-hydroxycyclohexa-2,4-dienones, which cyclodimerize via a bispericyclic Diels-Alder reaction. The involvement of catalytic or dirigent proteins in this process is still a question, but the cyclodimerization of ortho-quinols can be chemically reproduced in the laboratory with the same level of regioselectivity and stereoselectivity.
Many natural products of plant or microbial origins are derived from enzymatic dearomative oxygenation of 2-alkylphenolic precursors into 6-alkyl-6-hydroxycyclohexa-2,4-dienones. These so-called ortho-quinols cyclodimerize via a remarkably selective bispericyclic Diels-Alder reaction. Whether or not the intervention of catalytic or dirigent proteins is involved during this final step of the biosynthesis of these natural products, this cyclodimerization of ortho-quinols can be chemically reproduced in the laboratory with the same strict level of site-specific regioselectivity and stereoselectivity. This unique yet unified process, which finds its rationale in the inherent chemical reactivity of those ortho-quinols, is illustrated herein by an efficient and bioinspired first chemical synthesis of one of the most structurally complex and synthetically challenging examples of such natural cyclodimers, the bisditerpenoid (+)-maytenone.
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