Synthesis 2015; 47(07): 924-933
DOI: 10.1055/s-0034-1380157
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© Georg Thieme Verlag Stuttgart · New York

Temperature-Dependent Direct Enantioconvergent Silylation of a Racemic Cyclic Allylic Phosphate by Copper(I)-Catalyzed Allylic Substitution

Lukas B. Delvos
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany   eMail: martin.oestreich@tu-berlin.de
,
Martin Oestreich*
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany   eMail: martin.oestreich@tu-berlin.de
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Publikationsverlauf

Received: 16. Januar 2015

Accepted: 19. Januar 2015

Publikationsdatum:
23. Februar 2015 (eFirst)

Abstract

The near-quantitative transformation of a racemic cyclic allylic phosphate to a highly enantiomerically enriched allylic silane by allylic substitution with a silicon nucleophile is reported. The reaction is catalyzed by a chiral NHC–copper(I) complex. Experimental analysis revealed a rare case of a direct enantioconvergent transformation where the enantiomeric allylic phosphates converge to the same allylic silane by two distinctive SN2′ pathways with opposite diastereofacial selectivity.

Supporting Information

 
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