The Wender Cedrene Synthesis Revisited: A Catalytic Enantioselective Entry to the Chiral Key Intermediate

Julia Westphal; Christian Eric Schumacher; Hans-Günther Schmalz

doi:10.1055/s-0036-1588602

Synthesis, Inhaltsverzeichnis

Synthesis 2017; 49(01): 218-224
DOI: 10.1055/s-0036-1588602

paper

The Wender Cedrene Synthesis Revisited: A Catalytic Enantioselective Entry to the Chiral Key Intermediate

Authors

Julia Westphal

Department für Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany eMail: schmalz@uni-koeln.de
Christian Eric Schumacher

Department für Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany eMail: schmalz@uni-koeln.de
Hans-Günther Schmalz*

Department für Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany eMail: schmalz@uni-koeln.de

Abstract

Alle Artikel dieser Rubrik

Dedicated to Prof. Dr. Dieter Enders

Abstract

The seminal synthesis of the sesquiterpene (±)-α-cedrene reported by Wender in 1981 offers a uniquely short and elegant access to the bridged-tricyclic target compound by exploiting an intramolecular arene-olefin photocycloaddition. However, the synthesis was performed only in the racemic series so far. This synthesis was now re-investigated and the catalytic methods for the enantioselective preparation of the chiral key intermediate were evaluated. It was found that Cu-catalyzed allylic substitution of a cinnamyl chloride with MeMgBr in the presence of a Taddol-derived chiral phosphine-phosphite ligand affords the corresponding (1-methylallyl)arene with high enantioselectivity (94% ee). Hydroboration and subsequent Suzuki coupling gave (R)-curcuphenol methyl ether from which (–)-α-cedrene was prepared along the route paved by Wender.

Key words

terpenoids - total synthesis - enantioselectivity - asymmetric catalysis - allylation - photochemistry - copper - chiral P,P-ligands

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Referenzen

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