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Synlett 2010(6): 931-933  
DOI: 10.1055/s-0029-1219547
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A New Synthetic Methodology for the Pyrrolidine Ring

Dalila Beleia, Elena Bicua, Peter G. Jonesb, M. Lucian Birsa*a
a Department of Organic Chemistry, ‘Al. I. Cuza’ University of Iasi, 11 Carol I, 700506 Iasi, Romania
Fax: +40(232)201313; e-Mail: lbirsa@uaic.ro;
b Institute of Inorganic and Analytical Chemistry, Technical University of Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
Further Information

Publication History

Received 7 December 2009
Publication Date:
23 February 2010 (online)

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Abstract

An unprecedented synthesis of pyrrolidine rings has been accomplished by the reaction of azidoacetyl derivatives with maleate and fumarate esters.

Key words

azides - enamines - pyrrolidine - phenothiazine

    References and Notes

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  • 20a

    Crystal Structure Determination of 2a
    Crystal Data
    Monoclinic, space group P21/c, a = 8.9732 (3), b = 21.1876 (7), c = 13.1662 (4) Å, β = 94.560 (4)˚, Z = 4, T = 100 K.
    Data Collection
    A crystal ca. 0.3 × 0.25 × 0.2 mm³ was used to record 64269 intensities on a Oxford Diffraction Xcalibur E diffractometer using MoKα radiation (λ = 0.71073 Å).
    Structure Refinement
    The structure was refined anisotropically on F ² (program SHELXL-97)²0b to wR2 = 0.0854, R1 = 0.0346 for 351 parameters and 7192 unique reflexions. Data have been deposited in Cambridge under the number CCDC-756944.

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19

Analytical Data of Enamine 3a
Yield 0.28 g, 14%; R f = 0.47; mp 163-164 ˚C. IR (ATR): 2941, 1743, 1676, 1602, 1443, 1335, 1220, 1116, 754 cm-¹. ¹H NMR (400 MHz, CDCl3, TMS): δ = 3.66 (s, 3 H, CH3), 3.77 (s, 3 H, CH3), 4.39 (br s, 2 H, CH2), 5.40 (s, 1 H, CH), 7.23-7.54 (m, 8 H, 8 × CHar), 8.47 (s, 1 H, NH). ¹³C NMR (100 MHz, CDCl3, TMS): δ = 46.9 (t), 50.9 (q), 52.6 (q), 90.4 (d), 120.9 (s), 126.9 (d), 127.1 (d), 127.3 (d), 128.1 (d), 133.2 (s), 137.6 (s), 164.1 (s), 168.6 (s), 170.0 (s). MS (EI): m/z (%) = 398 (12)[M+], 331 (12), 199 (100). Anal. Calcd for C20H18N2O5S: C, 60.29; H, 4.55; N, 7.03. Found: C, 60.57; H, 4.61; N, 7.28.

21

Analytical Data of Pyrrolidine 2a
Yield 1.57 g, 58%; R f = 0.25; mp 192-193 ˚C. IR (ATR): 3342, 1734, 1723, 1675, 1432, 1342, 1297, 1031, 771, 755 cm-¹. ¹H NMR (400 MHz, CDCl3, TMS): δ = 2.75 (s, 2 H, CH2), 3.23 (s, 1 H, NH), 3.54 (s, 3 H, CH3), 3.62 (s, 3 H, CH3), 3.66 (m, 1 H, CH), 3.69 (s, 3 H, CH3), 3.75 (m, 1 H, CH), 3.79 (s, 3 H, CH3), 4.70 (m, 1 H, CH), 7.20-7.70 (m, 8 H, 8 × CHar). ¹³C NMR (100 MHz, CDCl3, TMS): δ = 40.2 (t), 51.4 (q), 51.9 (q), 52.1 (q), 52.2 (q), 53.0 (d), 59.0 (d), 69.3 (s), 126.3 (d), 126.9 (d), 127.0 (d), 127.3 (d), 127.4 (d), 127.8 (d), 128.1 (d), 133.5 (s), 133.4 (d), 138.0 (s), 138.2 (s), 170.3 (s), 170.4 (s), 170.6 (s), 171.1 (s), 173.1 (s). MS (EI): m/z (%) = 542 (5)[M+], 483 (3), 451 (3), 316 (16), 284 (12), 224 (18), 199 (100). Anal. Calcd for C26H26N2O9S: C, 57.56; H, 4.83; N, 5.16. Found: C, 57.79; H, 4.99; N, 5.47.