Synthesis, Table of Contents Synthesis 2018; 50(13): 2516-2522DOI: 10.1055/s-0037-1609717 paper © Georg Thieme Verlag Stuttgart · New York First Total Synthesis of 7-Isovaleryloxy-8-methoxygirinimbine Christian Brütting a Fakultät Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany Email: hans-joachim.knoelker@tu-dresden.de , Arndt W. Schmidt a Fakultät Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany Email: hans-joachim.knoelker@tu-dresden.de , Olga Kataeva b A. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya Str. 18, Kazan 420008, Russian Federation , Hans-Joachim Knölker* a Fakultät Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany Email: hans-joachim.knoelker@tu-dresden.de › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract We describe the first total synthesis of the pyrano[3,2-a]carbazole alkaloid 7-isovaleryloxy-8-methoxygirinimbine, using a palladium(II)-catalyzed double C–H-bond activation for construction of the carbazole framework and a phenylboronic acid catalyzed annulation of the pyran ring as key steps. Key words Key wordsalkaloids - annulation - catalysis - cyclization - natural products - palladium Full Text References References 1a Knölker H.-J. Reddy KR. Chem. Rev. 2002; 102: 4303 1b Chakraborty DP. Roy S. In Progress in the Chemistry of Organic Natural Products . Vol. 85. Herz W. Grisebach H. Kirby GW. Steglich W. Tamm C. Springer-Verlag; Vienna: 2003: 125 1c Knölker H.-J. Reddy KR. In The Alkaloids . Vol. 65. Cordell GA. Academic Press; Amsterdam: 2008: 1 1d Talluri KC. Nagarajan R. J. Chem. Sci. 2012; 124: 487 1e Chattopadhyay SK. Ghosh D. Mondal P. Ghosh SK. Synthesis 2012; 44: 2448 1f Pandit RP. Lee YR. Synthesis 2012; 44: 2910 1g Schmidt AW. Reddy KR. Knölker H.-J. Chem. Rev. 2012; 112: 3193 1h Roy J. Jana AK. Mal D. Tetrahedron 2012; 68: 6099 1i Ishikura M. Abe T. Choshi T. Hibino S. Nat. Prod. Rep. 2013; 30: 694 1j Vronteli A. Hadjipavlou-Litina DJ. Konstantinidou M. Litinas KE. ARKIVOC 2015; (iii): 111 1k Ishikura M. Abe T. Choshi T. Hibino S. Nat. Prod. Rep. 2015; 32: 1389 1l Padmaja P. Rao GK. Indrasena A. Reddy BV. S. Patel N. Shaik AB. Reddy N. Dubey PK. Bhadra MP. Org. Biomol. Chem. 2015; 13: 1404 1m Hou S. Liu Y. Kong Y. Brown ML. Org. Lett. 2015; 17: 2298 1n Kotha S. Ali R. Saifuddin M. Tetrahedron 2015; 71: 9003 1o Reddy KR. Reddy AS. Dhaked DK. Rasheed SK. Pathania AS. Shankar R. Malik F. Das P. Org. Biomol. Chem. 2015; 13: 9285 1p Kutz SK. Schmidt AW. Knölker H.-J. Synthesis 2017; 49: 275 2a Choi TA. Czerwonka R. Fröhner W. Krahl MP. Reddy KR. Franzblau SG. Knölker H.-J. ChemMedChem 2006; 1: 812 2b Rao LJ. M. Ramalakshmi K. Borse BB. Raghavan B. Food Chem. 2007; 100: 742 2c Choi TA. Czerwonka R. Forke R. Jäger A. Knöll J. Krahl MP. Krause T. Reddy KR. Franzblau SG. Knölker H.-J. Med. Chem. Res. 2008; 17: 374 2d Birari R. Javia V. Bhutani KK. Fitoterapia 2010; 81: 1129 2e Nagappan T. Ramasamy P. Wahid ME. A. Segaran TC. Vairappan CS. Molecules 2011; 16: 9651 2f Kok YY. Mooi LY. Ahmad K. Sukari MA. Mat N. Rahmani M. Ali AM. Molecules 2012; 17: 4634 2g Nagappan T. Segaran TC. Wahid ME. A. Ramasamy P. Vairappan CS. Molecules 2012; 17: 14449 2h Ma Q. Tian J. Yang J. Wang A. Ji T. Wang Y. Su Y. Fitoterapia 2013; 87: 1 2i Du Y.-Q. Liu H. Li C.-J. Ma J. Zhang D. Li L. Sun H. Bao X.-Q. Zhang D.-M. Fitoterapia 2015; 103: 122 2j Surineni G. Yogeeswari P. Sriram D. Kantevari S. Bioorg. Med. Chem. Lett. 2015; 25: 485 2k Surineni G. Yogeeswari P. Sriram D. Kantevari S. Med. Chem. Res. 2015; 24: 1298 2l Tan S.-P. Ali AM. Nafiah MA. Awang K. Ahmad K. Tetrahedron 2015; 71: 3946 2m Patel OP. S. Mishra A. Maurya R. Saini D. Pandey J. Taneja I. Raju KS. R. Kanojiya S. Shukla SK. Srivastava MN. Wahajuddin M. Tamrakar AK. Srivastava AK. Yadav PP. J. Nat. Prod. 2016; 79: 1276 2n Nalli Y. Khajuria V. Gupta S. Arora P. Riyaz-Ul-Hassan S. Ahmed Z. Ali A. Org. Biomol. Chem. 2016; 14: 3322 Pyrayafoline C, isolation: 3a Ito C. Nakagawa M. Wu T.-S. Furukawa H. Chem. Pharm. Bull. 1991; 39: 1668 Synthesis: 3b Hesse R. Jäger A. Schmidt AW. Knölker H.-J. Org. Biomol. Chem. 2014; 12: 3866 Murrayamine-J, isolation: 4a Wu T.-S. Wang M.-L. Wu P.-L. Ito C. Furukawa H. Phytochemistry 1996; 41: 1433 Synthesis: 4b Gassner C. Hesse R. Schmidt AW. Knölker H.-J. Org. Biomol. Chem. 2014; 12: 6490 Murrayamine-A (mukoenine-C), isolation: 5a Wu T.-S. Phytochemistry 1991; 30: 1048 5b Ito C. Thoyama Y. Omura M. Kajiura I. Furukawa H. Chem. Pharm. Bull. 1993; 41: 2096 Synthesis: 5c Julich-Gruner KK. Kataeva O. Schmidt AW. Knölker H.-J. Chem. Eur. J. 2014; 20: 8536 5d Schuster C. Julich-Gruner KK. Schnitzler H. Hesse R. Jäger A. Schmidt AW. Knölker H.-J. J. Org. Chem. 2015; 80: 5666 Koenigine, isolation: 6a Narasimhan NS. Paradkar MV. Kelkar SL. Indian J. Chem. 1970; 8: 473 6b Narasimhan NS. Paradkar MV. Chitguppi VP. Kelkar SL. Indian J. Chem. 1975; 13: 993 Synthesis: 6c Schuster C. Rönnefahrt M. Julich-Gruner KK. Jäger A. Schmidt AW. Knölker H.-J. Synthesis 2016; 48: 150 7a Iwai I. Ide J. Chem. Pharm. Bull. 1962; 10: 926 7b Iwai I. Ide J. Chem. Pharm. Bull. 1963; 11: 1042 7c Zsindely J. Schmid H. Helv. Chim. Acta 1968; 51: 1510 7d Hlubucek J. Ritchie E. Taylor WC. Tetrahedron Lett. 1969; 1369 7e Brown PE. Lewis RA. J. Chem. Soc., Perkin Trans. 1 1992; 573 7f Godfrey JD. Jr. Mueller RH. Sedergran TC. Soundararajan N. Colandrea VJ. Tetrahedron Lett. 1994; 35: 6405 8a Bissada S. Lau CK. Bernstein MA. Dufresne C. Can. J. Chem. 1994; 72: 1866 8b Chauder BA. Lopes CC. Lopes RS. C. da Silva AJ. M. Snieckus V. Synthesis 1998; 279 8c Dimakos V. Singh T. Taylor MS. Org. Biomol. Chem. 2016; 14: 6703 9 Sartori G. Casiraghi G. Bolzoni L. Casnati G. J. Org. Chem. 1979; 44: 803 10 Part 138 of Transition Metals in Organic Synthesis; for Part 137, see: Puls F. Knölker H.-J. Angew. Chem. Int. Ed. 2018; 57: 1222 ; Angew. Chem. 2018, 130, 1236 11 Mishra BB. Tiwari VK. Singh DD. Singh A. Tripathi VJ. Med. Chem. Res. 2006; 15: 119 12a Åkermark B. Eberson L. Jonsson E. Pettersson E. J. Org. Chem. 1975; 40: 1365 12b Knölker H.-J. O’Sullivan N. Tetrahedron 1994; 50: 10893 12c Hagelin H. Oslob JD. Åkermark B. Chem. Eur. J. 1999; 5: 2413 12d Krahl MP. Jäger A. Krause T. Knölker H.-J. Org. Biomol. Chem. 2006; 4: 3215 12e Forke R. Krahl MP. Krause T. Schlechtingen G. Knölker H.-J. Synlett 2007; 268 12f Forke R. Krahl MP. Däbritz F. Jäger A. Knölker H.-J. Synlett 2008; 1870 12g Liégault B. Lee D. Huestis MP. Stuart DR. Fagnou K. J. Org. Chem. 2008; 73: 5022 12h Zhang M. Adv. Synth. Catal. 2009; 351: 2243 12i Knölker H.-J. Chem. Lett. 2009; 38: 8 12j Song JJ. Reeves JT. Fandrick DR. Tan Z. Yee NK. Senanayake CH. ARKIVOC 2010; (i): 390 12k Forke R. Gruner KK. Knott KE. Auschill S. Agarwal S. Martin R. Böhl M. Richter S. Tsiavaliaris G. Fedorov R. Manstein DJ. Gutzeit HO. Knölker H.-J. Pure Appl. Chem. 2010; 82: 1975 12l Bauer I. Knölker H.-J. Top. Curr. Chem. 2012; 309: 203 12m Gensch T. Rönnefahrt M. Czerwonka R. Jäger A. Kataeva O. Bauer I. Knölker H.-J. Chem. Eur. J. 2012; 18: 770 12n Yoshikai N. Wei Y. Asian J. Org. Chem. 2013; 2: 466 12o Börger C. Schmidt AW. Knölker H.-J. Synlett 2014; 25: 1381 12p Julich-Gruner KK. Schmidt AW. Knölker H.-J. Synthesis 2014; 46: 2651 12q Hesse R. Krahl MP. Jäger A. Kataeva O. Schmidt AW. Knölker H.-J. Eur. J. Org. Chem. 2014; 4014 12r Schuster C. Börger C. Julich-Gruner KK. Hesse R. Jäger A. Kaufmann G. Schmidt AW. Knölker H.-J. Eur. J. Org. Chem. 2014; 4741 12s Hesse R. Kataeva O. Schmidt AW. Knölker H.-J. Chem. Eur. J. 2014; 20: 9504 12t Guo T. Huang F. Yu L. Yu Z. Tetrahedron Lett. 2015; 56: 296 12u Kober U. Knölker H.-J. Synlett 2015; 26: 1549 12v Hesse R. Schmidt AW. Knölker H.-J. Tetrahedron 2015; 71: 3485 12w Wen L. Tang L. Yang Y. Zha Z. Wang Z. Org. Lett. 2016; 18: 1278 12x Kutz SK. Börger C. Schmidt AW. Knölker H.-J. Chem. Eur. J. 2016; 22: 2487 12y Gensch T. Richter N. Theumer G. Kataeva O. Knölker H.-J. Chem. Eur. J. 2016; 22: 11186 13 Erickson PR. Grandbois M. Arnold WA. McNeill K. Environ. Sci. Technol. 2012; 46: 8174 14 Hesse R. Gruner KK. Kataeva O. Schmidt AW. Knölker H.-J. Chem. Eur. J. 2013; 19: 14098 15a Surry DS. Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338 15b Hartwig JF. Angew. Chem. Int. Ed. 1998; 37: 2046 15c Guram AS. Rennels RA. Buchwald SL. Angew. Chem., Int. Ed. Engl. 1995; 34: 1348 15d Louie J. Hartwig JF. Tetrahedron Lett. 1995; 36: 3609 16 Sheldrick GM. SHELXS-97, Programs for Crystal Structure Solution . University of Göttingen; Göttingen: 1997 17 Sheldrick GM. SADABS, v. 2.10, Bruker/Siemens Area Detector Absorption Correction Program. Bruker AXS Inc; Madison: 2002 18 Sheldrick GM. SHELXL-97, Programs for Crystal Structure Refinement . University of Göttingen; Göttingen: 1997 19 Farrugia L. J. Appl. Crystallogr. 1997; 30: 565 20 CCDC 1824776 (5) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. Supplementary Material Supplementary Material Supporting Information
