The enantioselective total synthesis of the actin-targeting metabolite (-)-microcarpalide is described. Key steps include ring-closing metathesis (RCM) for the final construction of the 10-membered lactone framework and stereoselective homologation of boronic esters for the insertion of all stereocentres with the desired absolute configuration. In particular, the acidic fragment was prepared in seven steps from a suitable chiral bromomethane boronate by means of two sequential stereoselective homologations to install the two stereocentres with the correct final R stereochemistry, employing (-)-pinanediol as the chiral director. Subsequent elaboration to the required C-7 backbone entailed nucleophilic displacement with a vinyl Grignard reagent, oxidative cleavage of the boronic scaffold and protection-deprotection manipulations. Interestingly, when the tribenzyloxy diene ester resulting from DCC-mediated coupling of the two key synthons was subjected to RCM in the presence of Grubbs´ catalyst, the reaction proceeded stereoselectively to yield the desired trans oxecin-2-one, albeit with poor conversion.

Enantioselective total synthesis of )-microcarpalide / Davoli, Paolo; Fava, Raffaele; Morandi, Stefania; Spaggiari, Alberto; Prati, Fabio. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 61:(2005), pp. 4427-4436.

Enantioselective total synthesis of )-microcarpalide

DAVOLI, Paolo;FAVA, Raffaele;MORANDI, Stefania;SPAGGIARI, Alberto;PRATI, Fabio
2005

Abstract

The enantioselective total synthesis of the actin-targeting metabolite (-)-microcarpalide is described. Key steps include ring-closing metathesis (RCM) for the final construction of the 10-membered lactone framework and stereoselective homologation of boronic esters for the insertion of all stereocentres with the desired absolute configuration. In particular, the acidic fragment was prepared in seven steps from a suitable chiral bromomethane boronate by means of two sequential stereoselective homologations to install the two stereocentres with the correct final R stereochemistry, employing (-)-pinanediol as the chiral director. Subsequent elaboration to the required C-7 backbone entailed nucleophilic displacement with a vinyl Grignard reagent, oxidative cleavage of the boronic scaffold and protection-deprotection manipulations. Interestingly, when the tribenzyloxy diene ester resulting from DCC-mediated coupling of the two key synthons was subjected to RCM in the presence of Grubbs´ catalyst, the reaction proceeded stereoselectively to yield the desired trans oxecin-2-one, albeit with poor conversion.
61
4427
4436
Enantioselective total synthesis of )-microcarpalide / Davoli, Paolo; Fava, Raffaele; Morandi, Stefania; Spaggiari, Alberto; Prati, Fabio. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 61:(2005), pp. 4427-4436.
Davoli, Paolo; Fava, Raffaele; Morandi, Stefania; Spaggiari, Alberto; Prati, Fabio
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/307116
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 34
  • ???jsp.display-item.citation.isi??? 32
social impact