The efficient and highly selective formation of a wide range of (hetero)cyclic cis-diol scaffolds using aminotriphenolate-based metal catalysts is reported. The key intermediates are cyclic carbonates, which are obtained in high yield and with high levels of diastereo- and chemoselectivity from the parent oxirane precursors and carbon dioxide. Deprotection of the carbonate structures affords synthetically useful cis-diol scaffolds with different ring sizes that incorporate various functional groups. This atom-efficient method allows the simple construction of diol synthons using inexpensive and accessible precursors and green metal catalysts and showcases the use of CO2 as a temporary protecting group. Protective Carbon: Aminotriphenolate complexes of FeIII and AlIII are highly efficient and selective catalysts for the conversion of functional (multi)cyclic oxiranes into the corresponding cis carbonates. Basic hydrolysis of the latter provides a series of useful cyclic cis-diol scaffolds in high yield. In this process, CO2 acts as both a temporary protecting group and an oxygen donor.

Carbon Dioxide as a Protecting Group: Highly Efficient and Selective Catalytic Access to Cyclic cis-Diol Scaffolds

Fiorani, Giulia
Writing – Original Draft Preparation
;
Kleij, Arjan W.
Conceptualization
2014-01-01

Abstract

The efficient and highly selective formation of a wide range of (hetero)cyclic cis-diol scaffolds using aminotriphenolate-based metal catalysts is reported. The key intermediates are cyclic carbonates, which are obtained in high yield and with high levels of diastereo- and chemoselectivity from the parent oxirane precursors and carbon dioxide. Deprotection of the carbonate structures affords synthetically useful cis-diol scaffolds with different ring sizes that incorporate various functional groups. This atom-efficient method allows the simple construction of diol synthons using inexpensive and accessible precursors and green metal catalysts and showcases the use of CO2 as a temporary protecting group. Protective Carbon: Aminotriphenolate complexes of FeIII and AlIII are highly efficient and selective catalysts for the conversion of functional (multi)cyclic oxiranes into the corresponding cis carbonates. Basic hydrolysis of the latter provides a series of useful cyclic cis-diol scaffolds in high yield. In this process, CO2 acts as both a temporary protecting group and an oxygen donor.
File in questo prodotto:
File Dimensione Formato  
Angew. Chem. Int. Ed. 2014, 53, 10416-10419.pdf

non disponibili

Descrizione: Published Article 25mar19
Tipologia: Versione dell'editore
Licenza: Accesso chiuso-personale
Dimensione 910.11 kB
Formato Adobe PDF
910.11 kB Adobe PDF   Visualizza/Apri

I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/3724519
Citazioni
  • ???jsp.display-item.citation.pmc??? 8
  • Scopus 167
  • ???jsp.display-item.citation.isi??? 159
social impact