A New Synthetic Methodology
for the Pyrrolidine Ring

Dalila Belei; Elena Bicu; Peter G. Jones; M. Lucian Birsa

doi:10.1055/s-0029-1219547

LETTER

A New Synthetic Methodology for the Pyrrolidine Ring

Dalila Belei^a, Elena Bicu^a, Peter G. Jones^b, 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

Abstract

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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

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Referenzen

References and Notes

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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 × CH_ar), 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.

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 mm^³ 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.

<A NAME="RD35409ST-20B">20b</A> Sheldrick GM. Acta Crystallogr., Sect. A.: Fundam. Crystallogr. 2008, 64: 112

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 × CH_ar). ^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.