Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2012; 23(15): 2251-2254
DOI: 10.1055/s-0031-1290457
DOI: 10.1055/s-0031-1290457
letter
Enantioselective Synthesis of Cryptopleurine and Boehmeriasin A via Organocatalytic Intramolecular Aza-Michael Addition
Further Information
Publication History
Received: 05 June 2012
Accepted after revision: 27 June 2012
Publication Date:
14 August 2012 (online)
Abstract
The enantioselective synthesis of phenanthroquinolizidine alkaloids cryptopleurine and boehmeriasin A was achieved in eight steps from commercial available Cbz-protected 2-piperidinone in 22% and 20% overall yield, respectively. The key steps of this route are intramolecular enantioselective aza-Michael addition, intramolecular aldol addition, and oxidative coupling.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Gellert E. J. Nat. Prod. 1982; 45: 50
- 1b Li Z, Jin Z, Huang R. Synthesis 2001; 2365
- 1c Chemler SR. Curr. Bioact. Compd. 2009; 5: 2
- 2a Niphakis MJ, Georg GI. Org. Lett. 2011; 13: 196
- 2b Wang K, Su B, Wang Z, Wu M, Li Z, Hu Y, Fan Z, Mi N, Wang Q. J. Agric. Food. Chem. 2010; 58: 2703
- 2c Stoye A, Opatz T. Org. Lett. 2010; 12: 2140
- 2d Pansare SV, Lingampally R, Dyapa R. Eur. J. Org. Chem. 2011; 2235
- 2e Yamashita S, Kurono N, Senboku H, Tokuda M, Orito K. Eur. J. Org. Chem. 2009; 1173
- 2f Wang K, Su B, Wang Z, Wu M, Li Z, Hu Y, Fan Z, Mi N, Wang Q. J. Agric. Food Chem. 2009; 58: 2703
- 2g Li ST, Han L, Sun L, Zheng D, Liu J, Fu YB, Huang XS, Wang ZY. Molecules 2009; 14: 5042
- 2h Cui MB, Wang QM. Eur. J. Org. Chem. 2009; 5445
- 3a Yan J, Luo D, Luo Y, Gao X, Zhang G. Int. J. Gynecol. Cancer 2006; 16: 165
- 3b Wei H, Yan J, Liu J, Luo D, Zhang J, Gao X. J. Med. Plants Res. 2009; 3: 35
- 4 Luo Y, Liu Y, Luo D, Gao X, Li B, Zhang G. Planta Med. 2003; 69: 842
- 5a Cui M, Wang Q. Eur. J. Org. Chem. 2009; 5445
- 5b Wang Z, Wang Q. Tetrahedron Lett. 2010; 51: 1377
- 5c Dumoulin D, Lebrun S, Couture A, Deniau E, Grandclaudon P. Eur. J. Org. Chem. 2010; 1943
- 5d Leighty M, Georg GI. ACS Med. Chem. Lett. 2011; 2: 313
- 6a De La Lande IS. Aust. J. Exp. Biol. Med. Sci. 1948; 26: 181
- 6b Gellert E, Riggs NV. Aust. J. Chem. 1954; 7: 113
- 6c Yang X, Shi Q, Bastow KF, Lee KH. Org. Lett. 2010; 12: 1416
- 6d Cui M, Song H, Feng A, Wang Z, Wang Q. J. Org. Chem. 2010; 75: 7018
- 6e Kim S, Lee T, Lee E, Lee J, Fan GJ, Lee SK, Kim D. J. Org. Chem. 2004; 69: 3144
- 6f Fürstner A, Kennedy JW. Chem.–Eur. J. 2006; 12: 7398
- 6g Kim S, Lee YM, Lee J, Lee T, Fu Y, Song Y, Cho J, Kim D. J. Org. Chem. 2007; 72: 4886
- 6h Suzuki H, Aoyagi S, Kibayashi C. J. Org. Chem. 1995; 60: 6114
- 7a Liu M, Sibi MP. Tetrahedron 2002; 58: 7991
- 7b Xu L.-W, Xia C.-G. Eur. J. Org. Chem. 2005; 633
- 7c Vicario JL, Bada D, Carrillo L. Synthesis 2007; 2065
- 7d Krishna PR, Sreeshailam A, Srinivas R. Tetrahedron 2009; 65: 9657
- 7e Enders D, Wang C, Liebich JX. Chem.–Eur. J. 2009; 15: 11058
- 8a Takasu K, Maiti S, Ihara M. Heterocycles 2003; 59: 51
- 8b Fustero S, Jimenez D, Moscardo J, Catalan S, del Pozo C. Org. Lett. 2007; 9: 5283
- 8c Carlson EC, Rathbone LK, Yang H, Collett ND, Carter RG. J. Org. Chem. 2008; 73: 5155
- 8d Fustero S, Moscardo J, Jimenez D, Perez-Carrion MD, Sanchez-Rosello M, del Pozo C. Chem.–Eur. J. 2008; 14: 9868
- 8e Cai Q, Zheng C, You S.-L. Angew. Chem. Int. Ed. 2010; 49: 8666
- 8f Yin Q, You S.-L. Chem. Sci. 2011; 2: 1344
- 9a Liu J.-D, Chen Y.-C, Zhang G.-B, Li Z.-Q, Chen P, Du J.-Y, Tu Y.-Q, Fan C.-A. Adv. Synth. Catal. 2011; 353: 2721
- 9b Fustero S, del Pozo C, Mulet C, Lazaro R, Sanchez-Rosello M. Chem.–Eur. J. 2011; 17: 14267
- 10 Yoshitomi Y, Arai H, Makino K, Hamada Y. Tetrahedron 2008; 64: 11568
- 11 Kimball FS, Turunen BJ, Ellis KC, Himes RH, Georg GI. Bioorg. Med. Chem. 2008; 16: 4367
- 12 The Physical Data of the Synthetic (R)-Cryptopleurine (1a) [α]D 20 –78.8 (c 0.5, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.88 (s, 2 H), 7.77 (d, J = 9.0 Hz, 1 H), 7.22–7.14 (m, 2 H), 4.42 (d, J = 15.6 Hz, 1 H), 4.09 (s, 3 H), 4.05 (s, 3 H), 4.00 (s, 3 H), 3.61 (d, J = 15.6 Hz, 1 H), 3.27 (d, J = 10.8 Hz, 1 H), 3.05 (d, J = 16.3 Hz, 1 H), 2.97–2.78 (m, 1 H), 2.53–2.16 (m, 2 H), 2.10–2.02 (m, 1 H), 1.94–1.69 (m, 2 H), 1.67–1.32 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 157.4, 149.4, 148.3, 130.1, 126.4, 125.2, 124.3, 124.0, 123.5, 123.4, 114.8, 104.7, 103.8, 57.5, 56.13, 56.0, 55.9, 55.7, 55.5, 34.4, 33.5, 25.7, 24.2. IR: νmax = 2930, 2915, 2910, 1700, 1683, 1610, 1511, 1470, 1466, 1455, 1450, 1440, 1435, 1417, 1405, 1270, 1255, 1231, 1188, 1177, 1152, 1130, 1124, 1101, 1072, 1041, 1022, 1012, 845, 833, 809, 783, 761, 634 cm–1. ESI-HRMS: m/z calcd for C24H28NO3 [M + H]+: 378.2069; found: 378.2087.
- 13 The Physical Data of the Synthetic (R)-Boehmeriasin A (1b) [α]D 27 –66.1 (c 0.15, MeOH). 1H NMR (400 MHz, CDCl3): δ = 7.95–7.84 (m, 3 H), 7.20 (dd, J = 9.0, 2.5 Hz, 1 H), 7.10 (s, 1 H), 4.34 (d, J = 15.3 Hz, 1 H), 4.09 (s, 3 H), 4.04 (s, 3 H), 4.00 (s, 3 H), 3.61 (d, J = 14.8 Hz, 1 H), 3.29 (d, J = 11.1 Hz, 1 H), 3.16 (dd, J = 16.7, 3.1 Hz, 1 H), 2.98–2.91 (m, 1 H), 2.44–2.24 (m, 2 H), 2.06–1.96 (m, 1 H), 1.92–1.71 (m, 3 H), 1.60–1.36 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 157.6, 149.4, 148.2, 130.3, 125.8, 125.1, 125.01, 124.9, 123.3, 114.8, 104.6, 104.0, 103.0, 57.5, 56.3, 56.98, 55.96, 55.5, 34.4, 33.5, 25.8, 24.2. IR: νmax = 2916, 1670, 1604, 1514, 1501, 1470, 1448, 1415, 1410, 1372, 1274, 1256, 1232, 1169, 1138, 1133, 1124, 1098, 1093, 1070, 1035, 1013, 999, 966, 941, 904, 844, 805, 796, 785, 760, 735 cm–1. ESI-HRMS: m/z calcd for C24H28NO3 [M + H]+: 378.2069; found: 378.2131.
For selected recent examples, see:
For isolation of cryptopleurine, see:
For a recent asymmetric syntheses of cryptopleurine, see:
For recent reviews on asymmetric aza-Michael addition, see:
For recent examples on organocatalytic intramolecular aza-Michael addition, see: