Biomimetic-inspired synthesis of sporochartines through Diels–Alder reaction between enantiopure (−)-sporothriolide and (+)-trienylfuranol A - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organic Chemistry Frontiers Année : 2023

Biomimetic-inspired synthesis of sporochartines through Diels–Alder reaction between enantiopure (−)-sporothriolide and (+)-trienylfuranol A

Résumé

A biomimetic-inspired synthesis of sporochartines A–D involving a [4 + 2] Diels-Alder cycloaddition between (−)-sporothriolide and (+)-trienylfuranol A is described. For this study, we have realized the first enantiopure total synthesis of (+)-trienylfuranol A, containing an unusual and very sensitive terminal trienyl moiety. In this synthetic study, we have performed for the first time baker's yeast-mediated reduction of α-oxo-γ-butyrolactone derivatives with high stereoselectivities. To improve the enantioselectivity level, an enzymatic kinetic resolution with Amano lipase PS, from Burkholderia cepacia, allowed us to prepare (+)-trienylfuranol A with excellent enantiomeric excess (>99%). A Diels-Alder reaction between the two secondary metabolites (−)-sporothriolide and (+)-trienylfuranol A allowed us to observe the formation of sporochartines in 39% isolated yield. The relative distribution of the sporochartines formed showed a spectacular correlation with that obtained from the fermentation culture of Hypoxylon monticulosum CLL-205 and allowed us to confirm that a Diels-Alder reaction is involved in the biosynthetic pathway for the formation of spiranic backbones of sporochartines.
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hal-04163470 , version 1 (17-07-2023)

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Guillaume Arcile, Théo Massard, Elsa van Elslande, Jamal Ouazzani, Jean-François Betzer. Biomimetic-inspired synthesis of sporochartines through Diels–Alder reaction between enantiopure (−)-sporothriolide and (+)-trienylfuranol A. Organic Chemistry Frontiers, In press, 10, pp.4111-4121. ⟨10.1039/d3qo00971h⟩. ⟨hal-04163470⟩
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