Subscribe to RSS
Download PDF
DOI: 10.1055/s-2007-986672
Enantioselective Total Synthesis of (-)-trans-Dendrochrysine via a Ring-Rearrangement Metathesis Approach
Publication History
Publication Date:
12 September 2007 (online)
Abstract
The enantioselective total synthesis of the dipyrrolidine alkaloid (-)-trans-dendrochrysine was accomplished in 18 steps starting from tropone. The key step was a ring-rearrangement metathesis for the construction of the bisheterocyclic skeleton of the natural product in a single step.
Key words
total synthesis - olefin metathesis - ruthenium - heterocycles - alkaloids
- 1
Lüning B.Leander K. Acta Chem. Scand. 1965, 19: 1607 - 2
Elander M. Chem. Commun. Univ. Stockholm 1973, 6: 3 - 3a
Grubbs RH.Chang S. Tetrahedron 1998, 54: 4413Reference Ris Wihthout Link - 3b
Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012Reference Ris Wihthout Link - 3c
Connon SJ.Blechert S. Angew. Chem. Int. Ed. 2003, 42: 1900Reference Ris Wihthout Link - 4a
Trnka TM.Grubbs RH. Acc. Chem. Res. 2001, 34: 18Reference Ris Wihthout Link - 4b
Scholl M.Ding S.Lee CW.Grubbs RH. Org. Lett. 1999, 1: 953Reference Ris Wihthout Link - 5
Handbook of Metathesis
Grubbs RH. Wiley-VCH; Weinheim: 2003.Reference Ris Wihthout Link - 6
Basra S.Blechert S. Strategies Tactics Org. Synth. 2004, 4: 315 - 7
Stapper C.Blechert S. J. Org. Chem. 2002, 67: 6456 - 8
Clennan EL. Tetrahedron 1991, 47: 1343 - 9
Johnson CR.Golebiowski A.Steensma DH. J. Am. Chem. Soc. 1992, 114: 9414 - 10
Hughes DL. Org. React. (N. Y.) 1992, 42: 335 - 11
Trost BM.Lee C. In Catalytic Asymmetric Synthesis Ojima I., Wiley-VCH; New York: 2000. p.593Reference Ris Wihthout Link - 12a
Schwab P.France MB.Ziller JW.Grubbs RH. Angew. Chem., Int. Ed. Engl. 1995, 34: 2039Reference Ris Wihthout Link - 12b
Schwab P.Grubbs RH.Ziller JW. J. Am. Chem. Soc. 1996, 118: 100Reference Ris Wihthout Link - 13a
Garber SB.Kingsbury JS.Gray BL.Hoveyda AH. J. Am. Chem. Soc. 2000, 122: 8168Reference Ris Wihthout Link - 13b
Gessler S.Randl S.Blechert S. Tetrahedron Lett. 2000, 41: 9973Reference Ris Wihthout Link - 14
Mori M.Sakakibara N.Kinoshita A. J. Org. Chem. 1998, 63: 6082Reference Ris Wihthout Link - 15
Banfi L.Cabri W.Poli G.Potenza D.Scolastico C. J. Org. Chem. 1987, 52: 5452 - 16
Dess DB.Martin JC. J. Org. Chem. 1983, 48: 4155 - 17
Frigerio M.Santagostino M. Tetrahedron Lett. 1994, 35: 8019 - 18
Millar JG.Oehlschlager AC.Wong JW. J. Org. Chem. 1983, 48: 4404
References and Notes
(-)-trans-Dendrochrysine: R f 0.30 (SiO2, hexanes-CH2Cl2-Et2NH, 10:4:1); [α]D 20 -9.2° (c = 0.25, CHCl3). 1H NMR (500 MHz, CDCl3, 323 K): δ = 1.19-2.16 (m, 8 H), 2.34 (s, 3 H), 2.39-2.65 (m, 3 H), 2.69-2.89 (m, 2 H), 2.98-3.11 (m, 1 H), 3.31 (ddd, J = 3.2, 9.0, 16.7 Hz, 1 H), 3.60-3.75 (m, 2 H), 4.49-4.68 (m, 1 H), 6.72 (d, J = 15.5 Hz, 1 H), 7.35-7.42 (m, 3 H), 7.51-7.56 (m, 2 H), 7.69 (d, J = 15.5 Hz, 1 H). 13C NMR (125 MHz, CDCl3, 353 K): δ = 22.3, 24.1 (br), 29.5, 31.4, 40.3, 45.5 (br), 46.9 (br), 47.8 (br), 53.9 (br), 56.6, 62.2, 119.4, 127.7, 128.7, 129.4, 135.7 (Cq), 141.8, 164.8 (Cq), 207.5 (Cq). IR (ATR): 2957 (m), 2927 (m), 2875 (m), 2852 (m), 2780 (m), 1708 (m), 1650 (s), 1605 (s), 1577 (m), 1497 (m), 1450 (m), 1415 (s), 1375 (m), 1347 (m), 1306 (m), 1259 (m), 1201 (m), 1185 (m), 764 (m) cm-1. MS (EI, 70 eV): m/z (%) = 340 [M+] (26), 279 (25), 278 (43), 277 (100), 209 (10), 201 (16), 199 (11), 183 (10), 167 (28), 150 (10), 149 (80), 140 (51), 131 (51), 126 (10), 124 (10), 103 (22), 98 (20), 97 (23), 85 (10), 84 (85), 83 (12). HRMS: m/z calcd for C21H28N2O2: 340.2151; found: 340.2155.