Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems

Nathan B. Bennett; Allen Y. Hong; Andrew M. Harned; Brian M. Stoltz

doi:10.1039/c1ob06189e

Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems

Nathan B. Bennett, Allen Y. Hong, Andrew M. Harned, Brian M. Stoltz

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	56-59
Number of pages	4
Journal	Org. Biomol. Chem.
Volume	10
Issue number	1
DOIs	https://doi.org/10.1039/c1ob06189e
State	Published - 2012
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-11-006-02
Acknowledgements: This 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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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title = "Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems",

abstract = "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.",

author = "Bennett, {Nathan B.} and Hong, {Allen Y.} and Harned, {Andrew M.} and Stoltz, {Brian M.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-006-02 Acknowledgements: This 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2012",

doi = "10.1039/c1ob06189e",

language = "English (US)",

volume = "10",

pages = "56--59",

journal = "Org. Biomol. Chem.",

issn = "1477-0520",

publisher = "Royal Society of Chemistry",

number = "1",

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AU - Bennett, Nathan B.

AU - Hong, Allen Y.

AU - Harned, Andrew M.

AU - Stoltz, Brian M.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-006-02 Acknowledgements: This 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2012

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AB - 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.

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ER -

Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems

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