Regioselective Synthesis of New 1-Aminopyrroles and 1-Amino-4,5,6,7-tetrahydroindoles by One-Pot ‘Conjugate Addition/Cyclization’ Reactions of 1,3-Bis(silyl enol ethers) with 1,2-Diaza-1,3-butadienes

Andreas Schmidt; Vahuni Karapetyan; Orazio A. Attanasi; Gianfranco Favi; Helmar Görls; Fabio Mantellini; Peter Langer

doi:10.1055/s-2007-990971

LETTER

Regioselective Synthesis of New 1-Aminopyrroles and 1-Amino-4,5,6,7-tetrahydroindoles by One-Pot ‘Conjugate Addition/Cyclization’ Reactions of 1,3-Bis(silyl enol ethers) with 1,2-Diaza-1,3-butadienes

Andreas Schmidt^a, Vahuni Karapetyan^a,b, Orazio A. Attanasi^c, Gianfranco Favi^c, Helmar Görls^d, Fabio Mantellini^c, Peter Langer*^a,e
^a Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
^b Faculty of Chemistry, Yerevan State University, Alex Manoogian 1, 0025 Yerevan, Armenia
^c Istituto di Chimica Organica, Università degli Studi di Urbino ‘Carlo Bo’, Via I Maggetti 24, 61029 Urbino, Italy
^d Institut für Anorganische und Analytische Chemie, Universität Jena, August-Bebel-Str. 2, 07740 Jena, Germany
^e Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
e-Mail: peter.langer@uni-rostock.de;

Abstract

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Abstract

Unknown functionalized 1-aminopyrroles and 1-amino-4,5,6,7-tetrahydroindoles were prepared under mild conditions and with excellent yields by one-pot ‘conjugate addition/cyclization’ reactions of 1,3-bis(silyl enol ethers) with 1,2-diaza-1,3-butadienes.

Key words

cyclizations - 1,2-diaza-1,3-butadienes - N-heterocycles - pyrroles - silyl enol ethers

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References

References and Notes

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General Procedure for the Synthesis of 3 and 5: To a CH₂Cl₂ solution (12 mL) of 1,2-diaza-1,3-butadiene 1 (2.0 mmol) was added 1,3-bis(silyl enol ether) 2 or 4 (2.4 mmol) and freshly dried ZnCl₂ (0.055 g, 0.4 mmol) at 20 °C. The solution was stirred for 12 h at r.t. and subsequently TFA (0.3 mL) was added. The solvent was removed in vacuo and the residue was purified by column chromatography [silica gel, heptane → heptane-EtOAc (30:70)].
Synthesis of 3d: Prepared from 1,2-diaza-1,3-butadiene 1a (0.370 g, 2.0 mmol), 1-tert-butoxy-1,3-bistrimethylsilyl-oxybuta-1,3-diene (2d; 0.726 g, 2.4 mmol) and ZnCl₂ (0.055 g, 0.4 mmol). Compound 3d was purified by chromatog-raphy and crystallized (EtOH) as a colorless solid (0.527 g, 81%); mp 178-180 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 1.25 (t, ³ J = 7.1 Hz, 3 H, CH₂CH ₃), 1.42 (s, 9 H, t-Bu), 2.29 (s, 3 H, CMe), 3.34 (dd, ² J = 17.0 Hz, 1 H, CCH₂), 3.44 (dd, ² J = 17.0 Hz, 1 H, CCH₂), 4.16 (q, ³ J = 7.1 Hz, 2 H, CH ₂CH₃), 6.19 (br, 2 H, CONH₂), 6.23 (s, 1 H, H_Hetar), 9.06 (s, 1 H, NNHCO). ¹³C NMR (62.9 MHz, DMSO-d ₆): δ = 10.5 (CH₂ CH₃), 14.6 (NCCH₃), 27.9 [C(CH₃)₃], 32.2 (CCH₂CO), 58.9 (OCH₂), 80.6 [OC(CH₃)₃], 106.2 (CH_Hetar), 108.7 (CCOO), 126.5, 136.6 (NC_Hetar), 157.2, 164.4, 169.1 (CO). IR (KBr): 3405 (s), 3270 (m), 2981 (m), 2934 (w), 2907 (w), 1740 (s), 1675 (s), 1576 (m), 1531 (m), 1477 (m), 1457 (m), 1414 (m), 1388 (m), 1371 (m), 1352 (m), 1229 (s), 1146 (s), 1081 (s), 1021 (w), 849 (w), 773 (w), 627 (w), 602 (w), 483 (w) cm^-1. MS (EI, 70 eV): m/z (%) = 325 (11) [M⁺], 269 (18), 224 (100), 207 (26), 166 (27), 57 (79). HRMS (EI, 70 eV): m/z [M]⁺ calcd for C₁₅H₂₃N₃O₅: 325.16322; found: 325.162992.

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