A general enantioselective route to the chamigrene natural product family

dc.contributor.authorWhite, David E.
dc.contributor.authorStewart, Ian C.
dc.contributor.authorSeashore-Ludlow, Brinton A.
dc.contributor.authorGrubbs, Robert H.
dc.contributor.authorStoltz, Brian M.
dc.contributor.institutionDivision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125.
dc.date.accessioned2016-02-25T12:29:37Z
dc.date.available2016-02-25T12:29:37Z
dc.date.issued2010-06
dc.description.abstractDescribed in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.
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). Additionally, the authors wish to thank the NIH-NIGMS (R01 GM080269-01, postdoctoral fellowships to D.E.W. and I.C.S.), Abbott, Amgen, Bristol-Myers Squibb, Merck, and Caltech for generous funding; Materia, Inc. for their kind donation of catalyst 49 used in these studies; Professors Mercedes Cueto and Karen L. Erickson for their kind donation of natural samples of elatol (1); Professor Adusumilli Srikrishna for copies of <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectra of synthetic (+/-)-laurencenone C ((+/-)-8) and (+/-)-alpha-chamigrene ((+/-)-5): and Professor Peter B. Dervan and David M. Chenoweth for use of their HPLC. Finally, B.M.S. thanks all of his current and former co-workers and colleagues who have made working at Caltech over the past 10 years such an enjoyable experience. As evidenced by the collaborative nature of this project, the spectacular environment at Caltech is one-of-a-kind and second-to-none.
dc.identifier.citationWhite DE, Stewart IC, Seashore-Ludlow BA, Grubbs RH, Stoltz BM (2010) A general enantioselective route to the chamigrene natural product family. Tetrahedron 66: 4668–4686. Available: http://dx.doi.org/10.1016/j.tet.2010.04.128.
dc.identifier.doi10.1016/j.tet.2010.04.128
dc.identifier.issn0040-4020
dc.identifier.journalTetrahedron
dc.identifier.pmcidPMC2925317
dc.identifier.pmid20798895
dc.identifier.urihttp://hdl.handle.net/10754/597276
dc.publisherElsevier BV
dc.titleA general enantioselective route to the chamigrene natural product family
dc.typeArticle
display.details.left<span><h5>Type</h5>Article<br><br><h5>Authors</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=White, David E.,equals">White, David E.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Stewart, Ian C.,equals">Stewart, Ian C.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Seashore-Ludlow, Brinton A.,equals">Seashore-Ludlow, Brinton A.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Grubbs, Robert H.,equals">Grubbs, Robert H.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Stoltz, Brian M.,equals">Stoltz, Brian M.</a><br><br><h5>KAUST Grant Number</h5>KUS-11-006-02<br><br><h5>Date</h5>2010-06</span>
display.details.right<span><h5>Abstract</h5>Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.<br><br><h5>Citation</h5>White DE, Stewart IC, Seashore-Ludlow BA, Grubbs RH, Stoltz BM (2010) A general enantioselective route to the chamigrene natural product family. Tetrahedron 66: 4668–4686. Available: http://dx.doi.org/10.1016/j.tet.2010.04.128.<br><br><h5>Acknowledgements</h5>This publication is based on work supported by Award No. KUS-11-006-02, made by King Abdullah University of Science and Technology (KAUST). Additionally, the authors wish to thank the NIH-NIGMS (R01 GM080269-01, postdoctoral fellowships to D.E.W. and I.C.S.), Abbott, Amgen, Bristol-Myers Squibb, Merck, and Caltech for generous funding; Materia, Inc. for their kind donation of catalyst 49 used in these studies; Professors Mercedes Cueto and Karen L. Erickson for their kind donation of natural samples of elatol (1); Professor Adusumilli Srikrishna for copies of <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectra of synthetic (+/-)-laurencenone C ((+/-)-8) and (+/-)-alpha-chamigrene ((+/-)-5): and Professor Peter B. Dervan and David M. Chenoweth for use of their HPLC. Finally, B.M.S. thanks all of his current and former co-workers and colleagues who have made working at Caltech over the past 10 years such an enjoyable experience. As evidenced by the collaborative nature of this project, the spectacular environment at Caltech is one-of-a-kind and second-to-none.<br><br><h5>Publisher</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.publisher=Elsevier BV,equals">Elsevier BV</a><br><br><h5>Journal</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.journal=Tetrahedron,equals">Tetrahedron</a><br><br><h5>DOI</h5><a href="https://doi.org/10.1016/j.tet.2010.04.128">10.1016/j.tet.2010.04.128</a><br><br><h5>PubMed ID</h5><a href="https://www.ncbi.nlm.nih.gov/pubmed/20798895">20798895</a><br><br><h5>PubMed Central ID</h5><a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2925317">PMC2925317</a></span>
kaust.grant.numberKUS-11-006-02
orcid.authorWhite, David E.
orcid.authorStewart, Ian C.
orcid.authorSeashore-Ludlow, Brinton A.
orcid.authorGrubbs, Robert H.
orcid.authorStoltz, Brian M.
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