An Enantioselective Mukaiyama Aldol Reaction as the Key Step towards the Tetrahydropyran Core of Psymberin via a γ-Butyrolactone Intermediate

Abstract

We report an alternative synthetic route towards the tetrahydropyran core of psymberin. The key steps are a catalytic enantioselective Mukaiyama aldol reaction and a syn reduction, which allowed for the rapid assembly of a γ-lactone as a precursor for the central fragment of the natural product.

Key words

aldol reaction - asymmetric catalysis - antitumor agent - lactone - enantioselectivity

• References

• 1 Cichewicz RH, Valeriote FA, Crews P. Org. Lett. 2004; 6: 1951
• 2 Pettit GR, Xu JP, Chapuis JC, Pettit RK, Tackett LP, Doubek DL, Hooper JN. A, Schmidt JM. J. Med. Chem. 2004; 47: 1149
• 3a Jiang X, Garcia-Fortanet J, De Brabander JK. J. Am. Chem. Soc. 2005; 127: 11254
• 3b Huang X, Shao N, Palani A, Aslanian R, Buevich A. Org. Lett. 2007; 9: 2597
• 3c Smith III AB, Jurica JA, Walsh SP. Org. Lett. 2008; 10: 5625
• 3d Crimmins MT, Stevens JM, Schaaf GM. Org. Lett. 2009; 11: 3990
• 3e Watanabe T, Imaizumi T, Chinen T, Nagumo Y, Shibuya M, Usui T, Kanoh N, Iwabuchi Y. Org. Lett. 2011; 12: 1040
• 3f Wan S, Wu F, Rech JC, Green ME, Balachandran R, Horne WS, Day BW, Floreancig PE. J. Am. Chem. Soc. 2011; 133: 16668
• 3g Byeon SR, Park H, Kim H, Hong J. Org. Lett. 2011; 13: 5816
• 4 Shangguan N, Kiren S, Williams LJ. Org. Lett. 2007; 9: 1093
• 5a Kiren S, Williams LJ. Org. Lett. 2005; 7: 2905
• 5b Green ME, Rech JC, Floreancig PE. Org. Lett. 2005; 7: 4117
• 5c Rech JC, Floreancig PE. Org. Lett. 2005; 7: 5175
• 5d Huang X, Shao N, Palani A, Aslanian R, Buevich A, Seidel-Dugan C, Huryk R. Tetrahedron Lett. 2008; 49: 3592
• 5e Lachance H, Marion O, Hall DG. Tetrahedron Lett. 2008; 49: 6061
• 5f Brown LE, Landaverry YR, Davies JR, Milinkevich KA, Ast S, Carlson JS, Oliver AG, Konopelski JP. J. Org. Chem. 2009; 74: 5405
• 5g Henßen B, Kasparyan E, Marten G, Pietruszka J. Heterocycles 2007; 245
• 5h Pietruszka J, Simon RC. Eur. J. Org. Chem. 2009; 3628
• 6a Piel J, Butzke D, Fusetani N, Hui D, Platzer M, Wen G, Matsunaga S. J. Nat. Prod. 2005; 68: 472
• 6b Fisch KM, Gurgui C, Heycke N, van der Sar SA, Anderson SA, Webb VL, Taudien S, Platzer M, Rubio BK, Robinson SJ, Crews P, Piel J. Nat. Chem. Biol. 2009; 5: 494
• 7a Mukaiyama T, Narasaka K, Banno K. Chem. Lett. 1973; 1011
• 7b Mukaiyama T, Banno K, Narasaka K. J. Am. Chem. Soc. 1974; 96: 7503
• 8a Lovchik MA, Goeke A, Fráter G. J. Org. Chem. 2007; 72: 2427
• 8b Lu Y, Woo SK, Krische MJ. J. Am. Chem. Soc. 2011; 133: 13876
• 9 Buffham WJ, Swain NA, Kostiuk SL, Gonçalves TP, Harrowven DC. Eur. J. Org. Chem. 2012; 1217

For an overview, see:
• 10a Molander GA In Science of Synthesis – Stereoselective Synthesis . Vol. 2. Liu L, Wang D, Li C.-J. Thieme; Stuttgart: 2011: 585
• 10b Mahrwald R. Chem. Rev. 1999; 99: 1095
• 10c Nelson SG. Tetrahedron: Asymmetry 1998; 9: 357
• 11 Carreira EM, Singer RA, Lee W. J. Am. Chem. Soc. 1994; 116: 8837
• 12 Dilman AD, Mayr H. Eur. J. Org. Chem. 2005; 1760
• 13 Inukai T, Yoshizawa R. J. Org. Chem. 1967; 32: 404
• 14 Bezzenine-Lafollée S, Guibé F, Villar H, Zriba R. Tetrahedron 2004; 60: 6931
• 15a Evans DA, Burgey CS, Kozlowski MC, Tregay SW. J. Am. Chem. Soc. 1999; 121: 686
• 15b Evans DA, MacMillan DW. C, Campos KR. J. Am. Chem. Soc. 1997; 119: 10859
• 16 Mikami K, Matsukawa S. J. Am. Chem. Soc. 1993; 115: 7039
• 17 Keck GE, Krishnamurthy D. J. Am. Chem. Soc. 1995; 117: 2363
• 18 Zimmer R, Schefzig L, Peritz A, Dekaris V, Reissig H.-U. Synthesis 2004; 1439
• 19 Chen K.-M, Hardtmann GE, Prasad K, Repič O, Shapiro MJ. Tetrahedron Lett. 1987; 28: 155