Total Synthesis and Absolute Stereochemical Assignment of ( )-Communesin F

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Total Synthesis and Absolute Stereochemical Assignment of ( )-Communesin F Zhiwei Zuo, Weiqing Xie, Dawei Ma* Shanghai Institute of rganic Chemistry, Shanghai, China J. Am. Chem. Soc. 2010, 132, 13226-13228. Marie-Céline Frantz Wipf Group - Current Literature September 25, 2010 Marie-Celine Frantz @ Wipf Group Page 1 of 10 9/26/2010

Communesin Familly Penicillium Marine alga Enteromorpha Intestinalis Emerging class of metabolites isolated from different marine and terrestrial species of the genus Penicillium. Communesins A and B first identified in 1993 by umata from a strain of Penicillium sp. isolated from the marine algae Enteromorpha intestinalis. 8 members disclosed to date (communesins A-). Indole polycyclic alkaloids with: 2 vicinal quaternary centers at C7/8 2 aminal moieties. Biological activity: moderate antiproliferative activity against several human leukemia cell lines active against brine shrimps antihelmintic activity insecticidal activity against silkworms microfilaments disruption. umata, A.; Takahashi, C.; Ito, Y.; Takada, T.; Kawai, K.; Usami, Y.; Matsumura, E.; Imachi, M.; Ito, T.; asegawa, T. Tetrahedron Lett. 1993, 34, 2355. Jadulco, R.; Edrada, R. A.; Ebel, R.; Berg, A.; Schauman, K.; Wray, V.; Steube, K.; Proksch, P. J. at. Prod. 2004, 67, 78. ayashi,.; Matsumoto,.; Akiyama, K. Biosci., Biotechnol., Biochem. 2004, 68, 753. Dalsgaard, P. W.; Blunt, J. W.; Munro, M.. G.; Frisvad, J. C.; Christophersen, C. J. at. Prod. 2005, 68, 258. Kerzaon, I.; Pouchus, Y. F.; Monteau, F.; Le Bizec, B.; ourrisson, M. R.; Biard, J. F.; Grovel,. Rapid Commun. Mass Spectrom. 2009, 23, 3928. Marie-Celine Frantz @ Wipf Group Page 2 of 10 9/26/2010

Communesins: Proposed Biosynthetic Pathways Stoltz and co-workers (2003) Mantle and co-workers (2006), further developed by Stoltz and May (2006) May, J. A.; Zeidan, R. K.; Stoltz, B. M. Tetrahedron Lett. 2003, 44, 1203. Wigley, L. J.; Mantle, P. G.; Perry, D. A. Phytochemistry 2006, 67, 561. May, J. A.; Stoltz, B. M. Tetrahedron 2006, 62, 5262. For a short review: Siengalewicz, P.; Gaich, T.; Mulzer, J. Angew. Chem. Int. Ed. 2008, 47, 8170. Marie-Celine Frantz @ Wipf Group Page 3 of 10 9/26/2010

Communesins: Synthetic Studies Stoltz and May (2006): Biomimetic model study of inverse-demand Diels-Alder Funk and Crawley (2006): Fluoride-promoted ring opening of aziridine followed by intramolecular hetero-diels-alder cycloaddition 2 2 C C 2 C 2 C 2 Teoc Cs 2 C 3 45% TMS TBAF 61% C 2 B C G AuCl(PPh 3 ) AgTf D May, J. A.; Stoltz, B. M. Tetrahedron 2006, 62, 5262. 89% Crawley, S. L.; Funk, R. L. rg. Lett. 2006, 8, 3995. F E For other studies: Crawley, S. L.; Funk, R. L. rg. Lett. 2003, 5, 3169. George, J..; Adlington, R. M. Synlett 2008, 2093. For total synthesis of related alkaloids: Artman III, G. D.; Weinreb, S. M. rg. Lett. 2003, 5, 1523. Fuchs, J. R.; Funk, R. L. J. Am. Chem. Soc. 2004, 126, 5068. Sabahi, A.; ovikov, A.; Rainier, J. D. Angew. Chem. Int. Ed. 2006, 45, 4317. Shen, L.; Zhang, M.; Wu, Y.; Qin, Y. Angew. Chem. Int. Ed. 2008, 47, 3618. For a short review: Siengalewicz, P.; Gaich, T.; Mulzer, J. Angew. Chem. Int. Ed. 2008, 47, 8170. C 2 Marie-Celine Frantz @ Wipf Group Page 4 of 10 9/26/2010

(±)-Communesin F: Qin's synthesis (2007) 5 steps from 4-bromoindole + 3 3 steps from isatin 2 intramolecular cyclopropanation CuTf F E C 88% 83% D 3 3 1.6:1 dr S 1-type cyclopropane opening PBu 3 aq. TF 8 1. PG 2. C8 epimerization shielded face [3,3] 1. [] 2. amination 3. lactamization A 1. amination 2. eck (µw) 3. a, -allylation C 2 isolated 84% C 2 C 2 Boc C 2 acid-catalyzed cyclization PPTS 66% (+ 21% diene) Boc G C 2 cyclization via imidate 1. BF 4 Et 3 2. TFA 3. Si 2 77% B C 2 1. K 2. ab 4, Ac 2 ( )-Communesin F - 30 steps (longest linear sequence) from commercially available material - 1.2% overall yield Yang, J.; Wu,.; Shen, L.; Qin, Y. J. Am. Chem. Soc. 2007, 129, 13794. Marie-Celine Frantz @ Wipf Group Page 5 of 10 9/26/2010

(±)-Communesin F: Weinreb's synthesis (2010) - 31 steps (longest linear sequence) from commercially available material - 0.9% overall yield Liu, P.; Seo, J..; Weinreb, S. M. Angew. Chem., Int. Ed. 2010, 49, 2000. Marie-Celine Frantz @ Wipf Group Page 6 of 10 9/26/2010

Title Paper: Communesin F Retrosynthetic Analysis Zuo, Z.; Xie, W.; Ma, D. J. Am. Chem. Soc. 2010, 132, 13226. Marie-Celine Frantz @ Wipf Group Page 7 of 10 9/26/2010

xidative coupling of indoles and pyrroles Baran's chanistic Rationale in Developing the xidative Indole (and Pyrrole) Coupling Reaction Application to the Total Synthesis of apalindole-type Alkaloids carvone indole, LiMDS; then Cu(II) 49-53% Application by Ma: Model Reaction for Intramolecular xidative Coupling CS hapalindole Q C fischerindole U Zuo, Z.; Xie, W.; Ma, D. J. Am. Chem. Soc. 2010, 132, 13226. Cl C fischerindole G Cl C fischerindole I Cl C welwitindolinone A Baran, P. S.; Richter, J. M. J. Am. Chem. Soc. 2004, 126, 7450. Baran, P. S.; Richter, J. M. J. Am. Chem. Soc. 2005, 127, 15394. Baran, P. S. Angew. Chem. Int. Ed. 2005, 44, 609. Baran, P. S.; DeMartino, M. P. Angew. Chem. Int. Ed. 2006, 45, 7083. Richter, J. M.; Whitefield, B. W.; Maimone, T. J.; Lin, D. W.; Castroviejo, M. P.; Baran, P. S. J. Am. Chem. Soc. 2007, 129, 12875. Richter, J. M.; Idhihara, Y.; Masuda, T.; Whitefield, B. W.; Llamas, T.; Pohjakallio, A.; Baran, P. S. J. Am. Chem. Soc. 2008, 130, 17938. Marie-Celine Frantz @ Wipf Group Page 8 of 10 9/26/2010

( )-Communesin F Total Synthesis: Title Paper - 19 steps (longest linear sequence) from commercially available material - 5.6% overall yield - Absolute configuration of natural Communesin F assigned: 6R,7R,8R,9S,11R. Zuo, Z.; Xie, W.; Ma, D. J. Am. Chem. Soc. 2010, 132, 13226. Marie-Celine Frantz @ Wipf Group Page 9 of 10 9/26/2010

Conclusion and Perspectives Concise asymmetric total synthesis of ( )-Communesin F. Absolute stereochemical assignment of natural Communesin F. Key steps: Comparison of synthetic routes (from commercially available materials): Qin Weinreb Ma Longest linear sequence (steps) 30 31 19 verall yield (%) 1.2 0.9 5.6 Perspectives: further applications of the spiro-fused indoline formation via an intramolecular oxidative coupling to the synthesis of related indole alkaloids. Marie-Celine Frantz @ Wipf Group Page 10 of 10 9/26/2010

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