Synthesis, Inhaltsverzeichnis Synthesis 2018; 50(04): 809-820DOI: 10.1055/s-0036-1591883 paper © Georg Thieme Verlag Stuttgart · New York Access to 5(6→7)abeo-Steroids through Benzilic Acid Rearrangement of i-Steroids Florian Noack Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany eMail: philipp.heretsch@fu-berlin.de , Bence Hartmayer Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany eMail: philipp.heretsch@fu-berlin.de , Philipp Heretsch * Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany eMail: philipp.heretsch@fu-berlin.de › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Dedicated to Barbara, Kurt, and Konrad Krieger Published as part of the Bürgenstock Special Section 2017 Future Stars in Organic Chemistry Abstract Benzilic acid rearrangement of i-steroid ketones and their subsequent opening gives access to 5(6→7)abeo-steroids. The functional group tolerance is demonstrated by several examples, including substrates with additional olefinic groups. The method opens a potential route to the synthesis of complex natural products such as solanioic acid from abundant steroid starting materials like ergosterol. Key words Key words abeo-steroids - benzilic acid rearrangement - i-steroids - natural products - total synthesis Volltext Referenzen References 1a Lin W.-H. Fang J.-M. Cheng Y.-S. Phytochemistry 1998; 48: 1391 1b Lu Y. Chen C.-X. Ni W. Hua Y. Liu H.-Y. Steroids 2010; 75: 982 2a Kasal A. Tetrahedron 2000; 56: 3559 2b Kasal A. Krištofíková Z. Buděšínský M. Tetrahedron 2007; 63: 11355 3 Ratnaweera PB. Williams DE. Patrick BO. de Silva ED. Andersen RJ. Org. Lett. 2015; 17: 2074 4 Liu J. Yang C. Zhang J. Wu J. Chen Y. Nat. Prod. Res. 2017; 31: 175 5 Cygan NK. Scheinost JC. Butters TD. Wentworth PJr. Biochemistry 2011; 50: 2092 6a Wentworth PJr. McDunn JE. Wentworth AD. Takeuchi C. Nieva J. Jones T. Bautista C. Ruedi JM. Gutierrez A. Janda KD. Babior BM. Eschenmoser A. Lerner RA. Science 2002; 298: 2195 6b Wentworth PJr. Wentworth AD. Zhu X. Wilson IA. Janda KD. Eschenmoser A. Lerner RA. Proc. Natl. Acad. Sci. U.S.A. 2003; 100: 1490 6c Babior BM. Takeuchi C. Ruedi J. Gutirrez A. Wentworth PJr. Proc. Natl. Acad. Sci. U.S.A. 2003; 100: 3031 6d Wentworth PJr. Nieva J. Takeuchi C. Galve R. Wentworth AD. Dilley RB. DeLaria GA. Saven A. Babior BM. Janda KD. Eschenmoser A. Lerner RA. Science 2003; 302: 1053 7a Brinkhorst J. Nara SJ. Pratt DA. J. Am. Chem. Soc. 2008; 130: 12224 7b Tomono S. Miyoshi N. Shiokawa H. Iwabuchi T. Aratani Y. Higashi T. Nukaya H. Ohshima H. J. Lipid Res. 2011; 52: 87 8a Wei X. Rodríguez AD. Wang Y. Franzblau SG. Bioorg. Med. Chem. Lett. 2008; 18: 5448 8b Gan C. Fan L. Cui J. Huang Y. Jiao Y. Wie W. Steroids 2012; 77: 1061 8c Cui J. Qi B. Gan C. Liu Z. Huang H. Lin Q. Zhao D. Huang Y. Mar. Drugs 2015; 13: 2488 9a Liu X. Pan X. Liang XT. Acta Chim. Sin. 1987; 45: 821 9b Guo JS. Liang XT. Chin. Chem. Lett. 1991; 2: 189 9c Guo JS. Liang XT. Youji Huaxue 1991; 11: 425 10 McMorris TC. Patil PA. J. Org. Chem. 1993; 58: 2338 11 Zhou W.-S. Zhou Y.-P. Jiang B. Synthesis 1989; 426 12a Stoltz BM. Wood JL. Tetrahedron Lett. 1996; 37: 3929 12b Burke AJ. Marques CS. Mini-Rev. Org. Chem. 2007; 4: 310 13a Schneider TF. Kaschel J. Werz DB. Angew. Chem. Int. Ed. 2014; 53: 5504 ; Angew. Chem. 2014, 126, 5608 13b Reissig H.-U. Small Ring Compounds in Organic Synthesis III. In Topics in Current Chemistry. Vol. 144. Springer; Berlin: 1988: 73 14a Heinze RC. Lentz D. Heretsch P. Angew. Chem. Int. Ed. 2016; 55: 11656 ; Angew. Chem. 2016, 128, 11828 14b Heinze RC. Heretsch P. Synlett 2017; 28: 1127 15 Zhang H.-B. Zhang H.-Y. Pan B.-C. Chin. Sci. Bull. 1990; 35: 420 16a Grenville V. Patel DK. Petrow V. Stuart-Webb A. Williamson DM. J. Chem. Soc. 1957; 4105 16b Litvinovskaya RP. Baranovsky AV. Averkova MA. Khripach VA. Russ. J. Bioorg. Chem. 2007; 33: 320 17 Marwah P. Marwah A. Lardy HA. Miyamoto H. Chang C. Bioorg. Med. Chem. 2006; 14: 5933 18 Monti L. Berliner DL. Jennings-White CL. Adams NW. (Pherin Pharmaceuticals, Inc.) PCT Int. Appl WO 02/089814 A1, 2002 Zusatzmaterial Zusatzmaterial Supporting Information
