Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems
KAUST Grant NumberKUS-11-006-02
Permanent link to this recordhttp://hdl.handle.net/10754/599838
MetadataShow full item record
AbstractA 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.
CitationBennett NB, Hong AY, Harned AM, Stoltz BM (2012) Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems. Org Biomol Chem 10: 56–59. Available: http://dx.doi.org/10.1039/c1ob06189e.
SponsorsThis publication is based on work supported by Award No. KUS-11-006-02, made by King Abdullah University of Science and Technology (KAUST). The authors wish to thank NIH-NIGMS (R01GM080269-01), Amgen, Abbott, Boehringer Ingelheim, and Caltech for financial support. AMH thanks the NIH for a postdoctoral fellowship. Materia, Inc. is gratefully acknowledged for the donation of catalysts. Michael Krout, Thomas Jensen, Christopher Henry, Scott Virgil, and Sarah Reisman are acknowledged for helpful discussions. David VanderVelde is acknowledged for critical NMR support.
PublisherRoyal Society of Chemistry (RSC)
JournalOrg. Biomol. Chem.
PubMed Central IDPMC3365663
CollectionsPublications Acknowledging KAUST Support
- Palladium-Catalyzed Asymmetric Alkylation in the Synthesis of Cyclopentanoid and Cycloheptanoid Core Structures Bearing All-Carbon Quaternary Stereocenters.
- Authors: Hong AY, Bennett NB, Krout MR, Jensen T, Harned AM, Stoltz BM
- Issue date: 2011 Dec 30
- Palladium-catalyzed asymmetric conjugate addition of arylboronic acids to five-, six-, and seven-membered β-substituted cyclic enones: enantioselective construction of all-carbon quaternary stereocenters.
- Authors: Kikushima K, Holder JC, Gatti M, Stoltz BM
- Issue date: 2011 May 11
- Organocatalytic and electrophilic approach to oxindoles with C3-quaternary stereocenters.
- Authors: Peng J, Huang X, Cui HL, Chen YC
- Issue date: 2010 Oct 1
- Asymmetric Friedel-Crafts alkylation of α-substituted β-nitroacrylates: access to β(2,2)-amino acids bearing indolic all-carbon quaternary stereocenters.
- Authors: Weng JQ, Deng QM, Wu L, Xu K, Wu H, Liu RR, Gao JR, Jia YX
- Issue date: 2014 Feb 7
- Gold-catalyzed asymmetric allylic substitution of free alcohols: an enantioselective approach to chiral chromans with quaternary stereocenters for the synthesis of vitamin E and analogues.
- Authors: Uria U, Vila C, Lin MY, Rueping M
- Issue date: 2014 Oct 20