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Enantioselective Construction of Vicinal Stereogenic Quaternary Centers by Dialkylation: Practical Total Syntheses of (+)- andmeso-Chimonanthine

2000; Wiley; Volume: 112; Issue: 1 Linguagem: Inglês

10.1002/(sici)1521-3757(20000103)112

1521-3757

Larry E. Overman, Jay F. Larrow, Brian A. Stearns, Jennifer M. Vance,

Asymmetric Synthesis and Catalysis

Angewandte ChemieVolume 112, Issue 1 p. 219-221 Zuschrift Enantioselective Construction of Vicinal Stereogenic Quaternary Centers by Dialkylation: Practical Total Syntheses of (+)- and meso-Chimonanthine Larry E. Overman Prof., Larry E. Overman Prof. [email protected] Search for more papers by this authorJay F. Larrow Dr., Jay F. Larrow Dr. Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this authorBrian A. Stearns, Brian A. Stearns Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this authorJennifer M. Vance, Jennifer M. Vance Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this author Larry E. Overman Prof., Larry E. Overman Prof. [email protected] Search for more papers by this authorJay F. Larrow Dr., Jay F. Larrow Dr. Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this authorBrian A. Stearns, Brian A. Stearns Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this authorJennifer M. Vance, Jennifer M. Vance Department of Chemistry University of California, Irvine 516 Rowland Hall, Irvine, CA 92697-2025, USA, Fax: (+1) 949-824-3866Search for more papers by this author First published: January 3, 2000 https://doi.org/10.1002/(SICI)1521-3757(20000103)112:1 3.0.CO;2-VCitations: 42AboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Alle drei Stereoisomere der hexacyclischen 3a,3a′-Bispyrrolidino[2,3-b]indolin-Einheit, die in einigen Indolalkaloiden vorkommt, können hergestellt werden, wie anhand der Totalsynthesen von meso-Chimonanthin 1 und (+)-Chimonanthin 2 gezeigt wurde. Kern der asymmetrischen Synthese des C2-symmetrischen Stereoisomers ist eine hoch diastereoselektive Alkylierung, die auf die Kombination eines prostereogenen Enolats mit einem chiralen Elektrophil zurückzuführen ist, das ein sp3-Kohlenstoffzentrum enthält. Supporting Information Hintergrundinformationen zu diesem Beitrag sind im WWW unter http://www.wiley-vch.de/contents/jc_2001/2000/z13956_s.pdf zu finden oder können beim Autor angefordert werden. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 Recent reviews of asymmetric synthesis of quaternary centers: a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402–415; 10.1002/(SICI)1521-3757(19980216)110:4 3.0.CO;2-6 Google Scholar Angew. Chem. Int. Ed. Engl. 1998, 37, 388–401; 10.1002/(SICI)1521-3773(19980302)37:4 3.0.CO;2-V PubMedWeb of Science®Google Scholar(b) K. Fuji, Chem. Rev. 1993, 93, 2037–2066. 10.1021/cr00022a005 CASWeb of Science®Google Scholar 2 For an excellent recent strategy, see R. M. Lemieux, A. I. Meyers, J. Am. Chem. Soc. 1998, 120, 5453–5457. 10.1021/ja9804159 CASWeb of Science®Google Scholar 3 Y. Adjibadé, B. Weniger, J. C. Quirion, B. Kuballa, P. Cabalion, R. Anton, Phytochemistry 1992, 31, 317–319. 10.1016/0031-9422(91)83062-P CASWeb of Science®Google Scholar 4 H. F. Hodson, B. Robinson, G. F. Smith, Proc. Chem. Soc. London 1961, 465–466. Google Scholar 5 T. Tokuyama, J. W. 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Google Scholar 15 Diol 10 had previously been converted into meso-chimonanthine.[12] The efficiency of this conversion is increased to 65% by utilizing the conditions we recently developed to convert a related chiral diol into (—)-chimonanthine.[13] Google Scholar 16 Consistent with this interpretation, stereoselection was eroded in thepresence of a sodium-selective cryptand (Kryptofix 221). Google Scholar 17 R. M. Williams, E. Kwast, Tetrahedron Lett. 1989, 30, 451–454. 10.1016/S0040-4039(00)95225-0 CASWeb of Science®Google Scholar 18 Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-134670. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: [email protected]). Google Scholar 19 Literature value:[6] [α]22/D=+264.5 (c=1.0 in EtOH). Google Scholar 20(a) A recent suryey of stereoselective C–C bond formation cites no examples in sections dealing with alkylation reactions with chiral electrophiles; see D. S. Matteson, Methoden Org. Chem. (Houben-Weyl) 4th ed. 1996, Vol. E21/2, pp. 1077–1118; (b) Interconversion of atropisomers of the dienolates derived from 6 is likely to be slow under the alkylation conditions. Whether the 20:1 selectivity arises solely in the initial alkylation step or enhanced by selective partitioning of the minor diastereomer in the cyclization strep has not yet6 been determined. Google Scholar Citing Literature Volume112, Issue1January 3, 2000Pages 219-221 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. ReferencesRelatedInformation