Synlett 2013; 24(20): 2763-2767
DOI: 10.1055/s-0033-1340012
letter
© Georg Thieme Verlag Stuttgart · New York

[3+2] Cycloaddition of Aziridines and Alkenes Catalyzed by a Cationic Manganese Porphyrin

Takuya Ozawa
a  Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
,
Takuya Kurahashi*
a  Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
b  JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan   Fax: +81(75)3832438   Email: kurahashi.takuya.2c@kyoto-u.ac.jp   Email: matsubara.seijiro.2e@kyoto-u.ac.jp
,
Seijiro Matsubara*
b  JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan   Fax: +81(75)3832438   Email: kurahashi.takuya.2c@kyoto-u.ac.jp   Email: matsubara.seijiro.2e@kyoto-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 03 September 2013

Accepted after revision: 16 September 2013

Publication Date:
05 November 2013 (online)


Abstract

A formal [3+2] cycloaddition between aziridines and alkenes to give the corresponding pyrrolidines was successfully carried out in the presence of a cationic manganese porphyrin catalyst. The use of the porphyrin catalyst allowed, for the first time, styrene derivatives to react with aziridines.

Supporting Information

 
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  • 14 Manganese Porphyrin Catalyzed [3+2] Cycloaddition of Aziridines and Alkenes; General Procedure A screw-cap vial was charged sequentially with [Mn(TPP)][SbF6] (0.02 mmol, 19 mg), aziridine 1 (0.2 mmol), alkene 2 (0.6 mmol), and anhyd DCE (0.8 mL) in a dry box. The vial was sealed and the mixture was stirred at 100 °C for 12 h. The mixture was then diluted with 10:1 hexane–EtOAc (3 mL) and passed through a short pad of silica gel, which was washed with 1:1 hexane–EtOAc (2 × 10 mL). The mixture was then concentrated in vacuo to give a crude product that was purified by flash column chromatography [silica gel, (20 g, 2 × 15 cm), hexane–EtOAc (5:1)]. 2-Phenyl-4-(4-tolyl)-1-tosylpyrrolidine (3aa) Colorless oil; yield: 58 mg (75%); TLC: Rf = 0.40 (hexane–EtOAc, 5:1). IR (neat): 3028, 2954, 2923, 2870, 1599, 1494, 1348, 1338, 1182, 1027, 814, 662 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.74–7.73 (m, 1.8 H) 7.65–7.64 (m, 2 H), 7.42–7.24 (m, 13.3 H), 7.11–7.02 (m, 5.8 H), 6.93–6.92 (m, 1.8 H), 5.06 (d, J = 8.0 Hz, 0.9 H), 4.81 (dd, J = 6.5, 10 Hz, 1 H), 4.17–4.14 (m, 1 H), 4.02 (dd, J = 7.5, 9.0 Hz, 0.9 Hz), 3.52–3.41 (m, 1.9 H), 3.28 (dd, J = 9.5, 10.5 Hz, 0.9 H), 2.97–2.89 (m, 1 H), 2.69–2.65 (m, 1 H), 2.46 (s, 2.7 H), 2.44 (s, 3 H), 2.32 (s, 3 H), 2.30 (s, 2.7 H), 2.18–2.14 (m, 0.9 H), 2.11–2.00 (m, 1.9 H). 13C NMR (125.7 MHz, CDCl3): δ = 143.4, 143.2, 142.9, 142.6, 136.7, 136.6, 136.5, 135.9, 135.8, 134.8, 129.6, 129.5, 129.3, 129.2, 128.4, 128.3, 127.6, 127.4, 127.2, 127.1, 126.8, 126.8, 126.4, 126.1, 64.5, 63.0, 55.9, 55.1, 44.4, 43.3, 42.1, 41.0, 21.5, 21.4, 20.9, 20.9. HRMS (ESI+): m/z [M + H]+ calcd for C24H26NO2S: 392.1679; found: 392.1663.