Concise Formal Synthesis of
(+)-Englerin A and Total Synthesis of (-)-Orientalol
F: Establishment of the Stereochemistry of the Organocatalytic [4+3]-Cycloaddition
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Chao-Lei Wang; Bing-Feng Sun; Shu-Guang Chen; Rui Ding; Guo-Qiang Lin; Jin-Yi Xu; Yong-Jia Shang

doi:10.1055/s-0031-1290090

LETTER

Concise Formal Synthesis of (+)-Englerin A and Total Synthesis of (-)-Orientalol F: Establishment of the Stereochemistry of the Organocatalytic [4+3]-Cycloaddition Reaction

Chao-Lei Wang^a,b, Bing-Feng Sun*^a, Shu-Guang Chen^a,c, Rui Ding^a, Guo-Qiang Lin*^a, Jin-Yi Xu*^b, Yong-Jia Shang^c
^a CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)54925081; e-Mail: bfsun@sioc.ac.cn; e-Mail: lingq@sioc.ac.cn.;
^b Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, 24 Tongjiaxiang, Nanjing 210009, P. R. of China
e-Mail: jinyixu@china.com;
^c College of Chemistry and Materials Science, Anhui Normal University, Beijing East Road No. 1, Wuhu 241000, P. R. of China

Abstract

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Abstract

The enantioselective formal synthesis of (+)-englerin A and the total synthesis of (-)-orientalol F were successfully accomplished via a triene. The success enabled establishment of the relative as well as absolute stereochemistry of the organocatalytic [4+3]-cycloaddition reaction.

Key words

asymmetric synthesis - chemoselectivity - regioselectivity - natural product - cycloaddition

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References

For reviews, see:

<A NAME="RW54411ST-1A">1a</A> Jacobsen EN. MacMillan DWC. Proc. Natl. Acad. Sci. U.S.A. 2010, 107: 20618 ; and references cited therein

<A NAME="RW54411ST-1B">1b</A> MacMillan DWC. Nature (London) 2008, 455: 304 ; and references cited therein

<A NAME="RW54411ST-1C">1c</A> Berkessel A. Groeger H. Asymmetric Organocatalysis Wiley-VCH; Weinheim: 2005.

For reviews and selected examples, see:

<A NAME="RW54411ST-2A">2a</A> Jones SB. Simmons B. Mastracchio A. MacMillan DWC. Nature (London) 2011, 475: 183

<A NAME="RW54411ST-2B">2b</A> Grondal C. Jeanty M. Enders D. Nat. Chem. 2010, 2: 167

<A NAME="RW54411ST-2C">2c</A> Jakubec P. Cockfield DM. Dixon DJ. J. Am. Chem. Soc. 2009, 131: 16632

<A NAME="RW54411ST-2D">2d</A> Jones SB. Simmons B. MacMillan DWC. J. Am. Chem. Soc. 2009, 131: 13606

<A NAME="RW54411ST-3A">3a</A> Harmata M. Ghosh SK. Hong X. Wacharasindhu S. Kirchhoefer P. J. Am. Chem. Soc. 2003, 125: 2058

For general and stereochemical aspects of the [4+3]-cycloaddition reaction, see:

<A NAME="RW54411ST-3B">3b</A> Krenske EH. Houk KN. Harmata M. Org. Lett. 2010, 12: 444

<A NAME="RW54411ST-3C">3c</A> Hartung IV. Hoffmann HMR. Angew. Chem. Int. Ed. 2004, 43: 1934

<A NAME="RW54411ST-3D">3d</A> Hoffmann HMR. Angew. Chem., Int. Ed. Engl. 1973, 12: 819

<A NAME="RW54411ST-4">4</A> Ohno M. Mori K. Hattori T. Eguchi S. J. Org. Chem. 1990, 55: 6086

<A NAME="RW54411ST-5A">5a</A> Ratnayake R. Covell D. Ransom TT. Gustafson KR. Beutler JA. Org. Lett. 2009, 11: 57

<A NAME="RW54411ST-5B">5b</A> Beutler JA, Ratnayake R, Covell D, and Johnson TR. inventors; WO 2009/088854.

<A NAME="RW54411ST-6A">6a</A> Willot M. Radtke L. Könning D. Fröhlich R. Gessner VH. Strohmann C. Christmann M. Angew. Chem. Int. Ed. 2009, 48: 9105

<A NAME="RW54411ST-6B">6b</A> Zhou Q. Chen X. Ma D. Angew. Chem. Int. Ed. 2010, 49: 3513

<A NAME="RW54411ST-6C">6c</A> Molawi K. Delpont N. Echavarren AM. Angew. Chem. Int. Ed. 2010, 49: 3517

<A NAME="RW54411ST-6D">6d</A> Nicolaou KC. Kang Q. Ng SY. Chen DY.-K. J. Am. Chem. Soc. 2010, 132: 8219

<A NAME="RW54411ST-6E">6e</A> Xu J. Caro-Diaz EJE. Theodorakis EA. Org. Lett. 2010, 12: 3708

<A NAME="RW54411ST-6F">6f</A> Sun B.-F. Wang C.-L. Ding R. Xu J.-Y. Lin G.-Q. Tetrahedron Lett. 2011, 52: 2155

<A NAME="RW54411ST-6G">6g</A> Chan KP. Chen DY.-K. ChemMedChem 2011, 6: 420

<A NAME="RW54411ST-6H">6h</A> Ushakov DB. Navickas V. Ströbele M. Maichle-Mössmer C. Sasse F. Maier ME. Org. Lett. 2011, 13: 2090

<A NAME="RW54411ST-6I">6i</A> Radtke LR. Willot M. Sun H. Ziegler S. Sauerland S. Strohmann C. Fröhlich R. Habenberger P. Waldmann H. Christmann M. Angew. Chem. Int. Ed. 2011, 50: 3998

<A NAME="RW54411ST-6J">6j</A> Li Z. Nakashige M. Chain WJ. J. Am. Chem. Soc. 2011, 133: 6553

<A NAME="RW54411ST-7A">7a</A> Peng G.-P. Tian G. Huang X.-F. Lou F.-C. Phytochemistry 2003, 63: 877

For related guaianes from the same source, see:

<A NAME="RW54411ST-7B">7b</A> Yoshikawa M. Yamaguchi S. Matsuda H. Kohda Y. Ishikawa H. Tanaka N. Yamahara J. Murakami N. Chem. Pharm. Bull. 1994, 42: 1813

<A NAME="RW54411ST-7C">7c</A> Yoshikawa M. Hatakeyama S. Tanaka N. Fukuda Y. Murakami N. Yamahara J. Chem. Pharm. Bull. 1992, 40: 2582

<A NAME="RW54411ST-8">8</A> Huang S.-X. Yang J. Xiao W.-L. Zhu Y.-L. Li R.-T. Li L.-M. Pu J.-X. Li X. Li S.-H. Sun H.-D. Helv. Chim. Acta 2006, 89: 1169

<A NAME="RW54411ST-9">9</A> For the synthesis of orientalol F and pubinernoid B using the gold-catalyzed cycloaddition of functionalized ketoenynes, see: Jiménez-Núñez E. Molawi K. Echavarren AM. Chem. Commun. 2009, 7327

<A NAME="RW54411ST-10A">10a</A> Traylor TG. Baker AW. J. Am. Chem. Soc. 1963, 85: 2746

<A NAME="RW54411ST-10B">10b</A> Brown HC. Kawakami JH. J. Am. Chem. Soc. 1973, 95: 8665

<A NAME="RW54411ST-10C">10c</A> Sokolova TN. Kartashov VR. Vasil’eva OV. Grishin YK. Russ. Chem. Bull. 1993, 42: 1583

For examples of the steric factor, see:

<A NAME="RW54411ST-11A">11a</A> Brown HC. Geoghegan JP. J. Org. Chem. 1970, 35: 1844

For examples of the electronic factor, see:

<A NAME="RW54411ST-11B">11b</A> Factor A. Traylor TG. J. Org. Chem. 1968, 33: 2607

<A NAME="RW54411ST-11C">11c</A> Krow G. Rodebaugh R. Grippi M. Carmosin R. Synth. Commun. 1972, 2: 211

<A NAME="RW54411ST-11D">11d</A> Mayo P. Orlova G. Goddard JD. Tam W. J. Org. Chem. 2001, 66: 5182

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