Stereoselective Total Synthesis of Paecilomycins E and F

This paper is dedicated to Oishika (the daughter of the senior author, B. Das) on the occasion of her 20^th birthday.

Abstract

The stereoselective total synthesis of two bioactive resorcylic acid lactones, paecilomycins E and F has been accomplished thorough a general pathway using cis-butene-1,4-diol as the starting material. The pivotal steps of the synthesis include Sharpless asymmetric epoxidation, Bestmann–Ohira alkynation, Jacobsen kinetic resolution, and Heck coupling reaction.

Key words

resorcylic acid lactones - paecilomycin E - paecilomycin F - total synthesis - cis-butene-1,4-diol

• References

• 1a Delmotte P, Delmotte-Plaquee J. Nature (London) 1953; 171: 344
• 1b Stob M, Baldwin RS, Tuite J, Andrews FN, Gillette KG. Nature (London) 1962; 196: 1318
• 1c Ellestad GA, Lovell FM, Perkinson NA, Hargreaves RT, McGahren WJ. J. Org. Chem. 1978; 43: 2339
• 1d Nair MS. R, Carey ST. Tetrahedron Lett. 1980; 21: 2011
• 1e Isaka M, Suyarnsestakorn C, Tanticharoen M, Kongsaeree P, Thebtaranonth Y. J. Org. Chem. 2002; 67: 1561
• 1f Hellwig V, Mayer-Bartschmid A, Muller H, Greif G, Kleymann G, Zitzmann W, Tichy H.-V, Stadler M. J. Nat. Prod. 2003; 66: 829
• 1g Winssinger N, Barluenga S. Chem. Commun. 2007; 22
• 1h Shining H, Kawamura Y, Ikeda A, Aoki M, Sakai N, Fujimoto N, Kawashima A. Tetrahedron 2009; 65: 3446
• 1i Xu LX, He ZX, Xue JH, Chen XP, Wei XY. J. Nat. Prod. 2010; 73: 885
• 1j Xu LX, He ZX, Xue JH, Chen XP, Wei XY. J. Nat. Prod. 2012; 75: 1006
• 1k Shao C.-L, Wu H.-X, Wang Ch.-Y, Liu Q.-A, Xu Y, Wei M.-Y, Qian P.-Y, Gu Y.-C, Zheng C.-J, She Z.-G, Lin Y.-C. J. Nat. Prod. 2013; 76: 302
• 2a Gaffoor I, Trail F. Appl. Environ. Microbiol. 2006; 72: 1793
• 2b Zhou H, Zhan J, Watanabe K, Xie X, Tang Y. Proc. Natl. Acad. Sci. U.S.A. 2008; 105: 6249
• 3a Navarro I, Basset JF, Hebbe S, Major SM, Werner T, Howsham C, Brackow J, Barett AG. M. J. Am. Chem. Soc. 2008; 130: 10293
• 3b Calo F, Richardson J, Barett AG. M. Org. Lett. 2009; 11: 4910
• 3c Sugiyama S, Fuse S, Takahasi T. Tetrahedron 2011; 67: 6654
• 3d Navickas V, Maier ME. Tetrahedron 2010; 66: 94
• 3e Srihari P, Mahankali B, Rajendraprasad K. Tetrahedron Lett. 2012; 53: 56
• 3f Hofmann T, Altmann KH. C.R. Chim. 2008; 11: 1318
• 3g Winssinger N, Fontaine JC, Barluenga S. Curr. Top. Med. Chem. 2009; 9: 1419
• 3h Jogireddy R, Dakas PY, Valot G, Barluenga S, Winssinger N. Chem. Eur. J. 2009; 15: 11498
• 3i Garbaccio RM, Stachel SJ, Baeschlin DK, Danishefsky SJ. J. Am. Chem. Soc. 2001; 123: 10903
• 3j Hofmann T, Altmarm KH. Synlett 2008; 1500
• 3k Baird LJ, Timmer MS, Teesdale-Spittle PH, Harvey JE. J. Org. Chem. 2009; 74: 2271
• 3l Barluenga S, Fontaine JG, Wang CH, Aoudi K, Chen RH, Beebe K, Neckers L, Winssinger N. ChemBioChem 2009; 10: 2753
• 3m Day JE. H, Blake AJ, Moody CJ. Synlett 2009; 1567
• 3n Takahashi T, Ikeda H, Tsuji J. Tetrahedron Lett. 1980; 21: 3885
• 3o Napolitano C, McArdle P, Murphy PV. J. Org. Chem. 2010; 75: 7404
• 3p Yang Z, Geng X, Solit D, Pratilas CA, Rosen N, Danishefsky SJ. J. Am. Chem. Soc. 2004; 126: 7881
• 3q Barluenga S, Dakas PY, Ferandin Y, Meijer L, Winssinger N. Angew. Chem. Int. Ed. 2006; 45: 3951
• 3r Geng X, Danishefsky SJ. Org. Lett. 2004; 6: 413
• 3s Chrovian CC, Knapp-Reed B, Montgomery J. Org. Lett. 2008; 10: 811
• 3t LeClair CA, Boxer MB, Thomas CJ, Maloney DJ. Tetrahedron Lett. 2010; 51: 6852
• 3u Miyatake-Ondozabal H, Barett AG. M. Org. Lett. 2010; 12: 5573
• 3v Martinez-Solorio D, Belmore KA, Jennings MP. J. Org. Chem. 2011; 76: 3898
• 3w Dakas P.-Y, Jogireddy R, Valot G, Barluenga S, Winssinger N. Chem. Eur. J. 2009; 15: 11490
• 3x Dakas P.-Y, Barluenga S, Totzke F, Zirrgiebel U, Winssinger N. Angew. Chem. Int. Ed. 2007; 46: 6899
• 3y Pal P, Jana N, Nanda S. Org. Biomol. Chem. 2014; 12: 8257
• 3z Jana N, Nanda S. Tetrahedron: Asymmetry 2012; 23: 802
• 4a Sudhakar Ch, Reddy PR, Kumar GC, Sujitha P, Das B. Eur. J. Org. Chem. 2012; 1253
• 4b Kashanna J, Jangili P, Kumar RA, Das B. Helv. Chim. Acta 2012; 95: 1666
• 4c Reddy GC, Balasubhramanyu P, Salvanna N, Reddy TS, Das B. Bioorg. Med. Chem. Lett. 2012; 22: 2415
• 4d Kumar JN, Das B. Tetrahedron Lett. 2013; 54: 3865
• 5a Katsuki T, Sharpless KB. J. Am. Chem. Soc. 1980; 102: 5974
• 5b Wang ZM, Zhou WS, Lin GQ. Tetrahedron Lett. 1985; 26: 6221
• 6 Mancuso AJ, Brownfain DS, Swern D. J. Org. Chem. 1979; 44: 4148
• 7a Muller S, Liepold B, Roth GJ, Bestmann JJ. Synlett 1996; 521
• 7b Callant P, D’Haenens L, Vandewalle M. Synth. Commun. 1984; 14: 155
• 8 Barluenga S, Moulin M, Lopez P, Winssinger N. Chem. Eur. J. 2005; 11: 4935
• 9 Onoda T, Shirai R, Kawai N, Iwasaki S. Tetrahedron 1996; 52: 13327
• 10 Yamaguchi M, Hirao I. Tetrahedron Lett. 1983; 24: 391
• 11 Chattopadhyay A, Dhotare B. Tetrahedron: Asymmetry 1998; 9: 2715
• 12 The inseparable mixture of diastereomeric alcohol was treated with MOMCl in the presence of DIPEA/DMAP (cat.) to furnish the corresponding MOM ethers. The products (diastereomers) at this stage were easily separated by flash chromatography. The percentage of diastereomers (9:1) was calculated based on the weight of the MOM-protected products.
• 13 Dushin RG, Danishefsky SJ. J. Am. Chem. Soc. 1992; 114: 655
• 14a Kamisuki S, Takahashi S, Mizushina Y, Hanashima S, Kuramochi K, Kobayashi S, Sakaguchi K, Nakata T, Sugawara F. Tetrahedron 2004; 60: 5695
• 14b Mitsunobu O. Synthesis 1981; 1
• 15a Heck RF. J. Am. Chem. Soc. 1968; 90: 5518
• 15b Mizoroki T, Mori K, Ozaki A. Bull. Chem. Soc. Jpn. 1971; 44: 581
• 15c Heck RF, Nolley JP. J. Org. Chem. 1972; 37: 2320
• 15d Fürstner A, Thiel OR, Kindler N, Bartkowska B. J. Org. Chem. 2000; 65: 7990
• 16a Bhattacharjee A, De Brabander JK. Tetrahedron Lett. 2000; 41: 8069
• 16b Nicolaou KC, Kim DW, Baati R. Angew. Chem. Int. Ed. 2002; 41: 3701
• 16c Hilli F, White JM, Rizzacasa MA. Tetrahedron Lett. 2002; 43: 8507
• 17 Schaus SE, Brandes BD, Larrow JF, Tokunaga M, Hansen KB, Gould AE, Furrow ME, Jacobsen EN. J. Am. Chem. Soc. 2002; 124: 1307