Org Lett. 2008 Oct 16;10(20):4509-12. Epub 2008 Sep 18.

Enantioselective syntheses of carbanucleosides from the Pauson-Khand adduct of trimethylsilylacetylene and norbornadiene.

Vázquez-Romero A, Rodríguez J, Lledó A, Verdaguer X, Riera A.

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Unitat de Recerca en Síntesi Asimètrica (URSA-PCB), Institute for Research in Biomedicine and Departament de Química Orgànica, Universitat de Barcelona, Parc Científic de Barcelona c/ Baldiri Reixac 10, 08028 Barcelona, Spain.

Abstract

A new enantioselective approach to carbanucleosides from Pauson-Khand (PK) adduct 1 is disclosed. The chiral cyclopentenone 1 is readily accessible in enantiomerically pure form via PK reaction of trimethylsilylacetylene and norbornadiene using N-benzyl-N-diphenylphosphino-tert-butyl-sulfinamide as a chiral P,S ligand. (-)-Carbavir and (-)-Abacavir were enantioselectively synthesized starting from (-)-1. The key steps of the sequence are a photochemical conjugate addition of a hydroxymethyl radical, a retro-Diels-Alder reaction, and a palladium catalyzed allylic substitution to introduce the nucleobase.

PMID:: 18798645; [PubMed - indexed for MEDLINE]

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