Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork-Danheiser approach: preparation of mono-, bi-, and tricyclic systems.
A general method for the synthesis of β-substituted and unsubstituted cycloheptenones bearing enantioenriched all-carbon γ-quaternary stereocenters is reported. Hydride or organometallic addition to a seven-membered ring vinylogous ester followed by finely tuned quenching parameters achieves elimination to the corresponding cycloheptenone. The resulting enones are elaborated to bi- and tricyclic compounds with potential for the preparation of non-natural analogs and whose structures are embedded in a number of cycloheptanoid natural products.
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, California Institute of Technology, Division of Chemistry and Chemical Engineering, Mail Code 101-20, Pasadena, CA 91125, USA.
Nathan B
NB
Bennett
Allen Y
AY
Hong
Andrew M
AM
Harned
Brian M
BM
Stoltz
D000478:Alkylation; D006536:Heptanes / Q000737:chemistry*; D013237:Stereoisomerism
D006536:Heptanes