Synthesis of (–)-Bulgecinine and 5-epi-Bulgecinine through Proline-Catalysed Asymmetric α-Hydroxylation of an Aldehyde Derived from l-Glutamic Acid

Abstract

A very efficient synthetic route to (–)-bulgecinine and 5-epibulgecinine from an aldehyde derived from l-glutamic acid is reported. Proline-catalysed asymmetric α-hydroxylation reaction of an aldehyde is the key step in this synthesis, which is used to incorporate a hydroxyl group at the α-position to that aldehyde in good yield and with very high diastereoselectivity. Both (–)-bulgecinine and 5-epi-bulgecinine are synthesised from the same olefin via epoxidation followed by BF₃·OEt₂-catalyzed intramolecular cyclisation. This synthetic route can easily be extended for the synthesis of the enantiomer and other isomers of bulgecinine starting from an aldehyde derived from d-glutamic acid.

Key words

asymmetric hydroxylation - organocatalysis - diastereoselectivity - glycopeptide - antibiotics

• References and notes

• 1 Shinagawa S, Maki M, Kintaka K, Imada A, Asai M. J. Antibiot. 1985; 38: 17
• 2 Imada A, Kintaka K, Nakao M, Shinagawa S. J. Antibiot. 1982; 35: 1400
• 3 Kraft AR, Prabhu J, Ursinus A, Holtje JV. J. Bacteriol. 1999; 181: 7192
• 4 Shinagawa S, Kashara F, Wada Y, Harada S, Asai M. Tetrahedron 1984; 40: 3465
• 5 Van Asselt EJ, Kalk KH, Dijkstra BW. Biochemistry 2000; 39: 1924
• 6 Thunnissen AM. W. H, Rozeboom HJ, Kalk KH, Dijkstra BW. Biochemistry 1995; 34: 12729
• 7 Templin MF, Edwards DH, Hoeltje JY. J. Biol. Chem. 1992; 267: 20039; and references therein
• 8 Das B, Kumar DN. Synlett 2011; 1285
• 9 Show K, Upadhyay PK, Kumar P. Tetrahedron: Asymmetry 2011; 22: 1234
• 10 Toumi M, Couty F, Evano G. Tetrahedron Lett. 2008; 49: 1175
• 11 Krasinski A, Jurczak J. Tetrahedron Lett. 2001; 42: 2019
• 12 Holt KA, Swift JP, Smith ME. B, Taylor SJ. C, McCague R. Tetrahedron Lett. 2002; 43: 1545
• 13 Khalaf JK, Dutta A. J. Org. Chem. 2004; 69: 387
• 14 Chavan SP, Praveen C, Sharma P, Kalkote UR. Tetrahedron Lett. 2005; 46: 439
• 15 Trost BM, Horne DB, Woltering MJ. Chem. Eur. J. 2006; 12: 6607
• 16 Chandrasekhar S, Chandrashekar G, Vijeendera K, Sarma GD. Tetrahedron: Asymmetry 2006; 17: 2864
• 17 Wang J.-T, Lin T.-C, Chen Y.-H, Lin C.-H, Fang J.-M. MedChemComm 2013; 4: 783
• 18 Natori Y, Kikuchi S, Kondo T, Saito Y, Yoshimura Y, Takahata H. Org. Biomol. Chem. 2014; 12: 1983
• 19a Venkataramasubramanian V, Chaithanya Kiran IN, Sudalai A. Synlett 2015; 26: 355
• 19b Kumar P, Dwivedi N. Acc. Chem. Res. 2013; 46: 289
• 19c Zhong G. Angew. Chem. Int. Ed. 2003; 42: 4247
• 19d Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007; 107: 5471
• 19e Vilaivan T, Bhanthumnavin W. Molecules 2010; 15: 917
• 19f Lalwani KG, Sudalai A. Synlett 2016; 27: 1339
• 19g Hayashi Y, Yamaguchi J, Hibino K, Shoji M. Tetrahedron Lett. 2003; 44: 8293
• 19h Mangion IK, MacMillan DW. C. J. Am. Chem. Soc. 2005; 127: 3696
• 19i Momiyama N, Yamamoto H. J. Am. Chem. Soc. 2003; 125: 6038
• 19j Lee LG, Whitesides GM. J. Org. Chem. 1986; 51: 25
• 19k Chacko S, Ramapanicker R. J. Org. Chem. 2015; 80: 4776
• 19l Brown SP, Brochu MP, Sinz CJ, MacMillan DW. C. J. Am. Chem. Soc. 2003; 125: 10808
• 20 Janey JM. Angew. Chem. Int. Ed. 2005; 44: 4292
• 21 Petakamsetty R, Jain VK, Majhi PK, Ramapanicker R. Org. Biomol. Chem. 2015; 13: 8512
• 22 Jain VK, Ramapanicker R. Tetrahedron 2017; 73: 1568
• 23 Petakamsetty R, Das RP, Ramapanicker R. Tetrahedron 2014; 70: 9554
• 24 Truchot C, Wang Q, Sasaki NA. Eur. J. Org. Chem. 2005; 1765
• 25 Xu Z, Zhang F, Zhang L, Jia Y. Org. Biomol. Chem. 2011; 9: 2512