Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

Handle URI:
http://hdl.handle.net/10754/599131
Title:
Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters
Authors:
Hong, Allen Y.; Bennett, Nathan B.; Krout, Michael R.; Jensen, Thomas; Harned, Andrew M.; Stoltz, Brian M.
Abstract:
General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.
Citation:
Hong AY, Bennett NB, Krout MR, Jensen T, Harned AM, et al. (2011) Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters. Tetrahedron 67: 10234–10248. Available: http://dx.doi.org/10.1016/j.tet.2011.10.031.
Publisher:
Elsevier BV
Journal:
Tetrahedron
KAUST Grant Number:
KUS-11-006-02
Issue Date:
Dec-2011
DOI:
10.1016/j.tet.2011.10.031
PubMed ID:
22347731
PubMed Central ID:
PMC3279929
Type:
Article
ISSN:
0040-4020
Sponsors:
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 (R01M080269-01), Amgen, Abbott, Boehringer Ingelheim, and Caltech for financial support. A.Y.H. thanks Roche for an Excellence in Chemistry Award and Abbott for an Abbott Scholars Symposium Award. M.R.K. acknowledges Eli Lilly for a predoctoral fellowship. T.J. thanks the Danish Council for Independent Research/Natural Sciences for a postdoctoral fellowship. Materia, Inc. is gratefully acknowledged for the donation of metathesis catalysts. Lawrence Henling and Dr. Michael Day are acknowledged for X-ray crystallographic structure determination. The Bruker KAPPA APEXII X-ray diffractometer used in this study was purchased via an NSF CRIF:MU award to Caltech (CHE-0639094). Prof. Sarah Reisman, Dr. Scott Virgil, Dr. Christopher Henry, and Dr. Nathaniel Sherden contributed with helpful discussions. Dr. David VanderVelde and Dr. Scott Ross are acknowledged for NMR assistance. The Varian 400 MR instrument used in this study was purchased via an NIH award to Caltech (NIH RR027690). Dr. Mona Shahgholi and Naseem Torian are acknowledged for high-resolution mass spectrometry assistance.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorHong, Allen Y.en
dc.contributor.authorBennett, Nathan B.en
dc.contributor.authorKrout, Michael R.en
dc.contributor.authorJensen, Thomasen
dc.contributor.authorHarned, Andrew M.en
dc.contributor.authorStoltz, Brian M.en
dc.date.accessioned2016-02-25T13:53:27Zen
dc.date.available2016-02-25T13:53:27Zen
dc.date.issued2011-12en
dc.identifier.citationHong AY, Bennett NB, Krout MR, Jensen T, Harned AM, et al. (2011) Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters. Tetrahedron 67: 10234–10248. Available: http://dx.doi.org/10.1016/j.tet.2011.10.031.en
dc.identifier.issn0040-4020en
dc.identifier.pmid22347731en
dc.identifier.doi10.1016/j.tet.2011.10.031en
dc.identifier.urihttp://hdl.handle.net/10754/599131en
dc.description.abstractGeneral catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.en
dc.description.sponsorshipThis 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 (R01M080269-01), Amgen, Abbott, Boehringer Ingelheim, and Caltech for financial support. A.Y.H. thanks Roche for an Excellence in Chemistry Award and Abbott for an Abbott Scholars Symposium Award. M.R.K. acknowledges Eli Lilly for a predoctoral fellowship. T.J. thanks the Danish Council for Independent Research/Natural Sciences for a postdoctoral fellowship. Materia, Inc. is gratefully acknowledged for the donation of metathesis catalysts. Lawrence Henling and Dr. Michael Day are acknowledged for X-ray crystallographic structure determination. The Bruker KAPPA APEXII X-ray diffractometer used in this study was purchased via an NSF CRIF:MU award to Caltech (CHE-0639094). Prof. Sarah Reisman, Dr. Scott Virgil, Dr. Christopher Henry, and Dr. Nathaniel Sherden contributed with helpful discussions. Dr. David VanderVelde and Dr. Scott Ross are acknowledged for NMR assistance. The Varian 400 MR instrument used in this study was purchased via an NIH award to Caltech (NIH RR027690). Dr. Mona Shahgholi and Naseem Torian are acknowledged for high-resolution mass spectrometry assistance.en
dc.publisherElsevier BVen
dc.titlePalladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocentersen
dc.typeArticleen
dc.identifier.journalTetrahedronen
dc.identifier.pmcidPMC3279929en
dc.contributor.institutionWarren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125.en
kaust.grant.numberKUS-11-006-02en
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