Enantioselective Total Synthesis of (-)-trans-Dendrochrysine via a Ring-Rearrangement Metathesis Approach

Maximilian Dochnahl; Sabrina Renate Schulz; Siegfried Blechert

doi:10.1055/s-2007-986672

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Synlett 2007(16): 2599-2601
DOI: 10.1055/s-2007-986672

LETTER

Enantioselective Total Synthesis of (-)-trans-Dendrochrysine via a Ring-Rearrangement Metathesis Approach

Maximilian Dochnahl, Sabrina Renate Schulz, Siegfried Blechert*
Fachgruppe Organische Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany
Fax: +49(30)31423619; e-Mail: blechert@chem.tu-berlin.de;

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Publikationsverlauf

Received 21 June 2007
Publikationsdatum:
12. September 2007 (online)

Abstract
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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

References and Notes

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19

(-)-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 (C_q), 141.8, 164.8 (C_q), 207.5 (C_q). 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.