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Synlett 2007(18): 2819-2822  
DOI: 10.1055/s-2007-990841
LETTER
© Georg Thieme Verlag Stuttgart · New York

Chemoselective Epoxidation of Ene-Ynamides: Intramolecular Cyclopropanation Induced by the Intermediate α-Oxocarbene

Sylvain Couty, Christophe Meyer*, Janine Cossy
Laboratoire de Chimie Organique, associé au CNRS, ESPCI, 10 Rue Vauquelin, 75231 Paris Cedex 05, France
Fax: +33(1)40794660; e-Mail: christophe.meyer@espci.fr; e-Mail: janine.cossy@espci.fr;
Further Information

Publication History

Received 28 July 2007
Publication Date:
12 October 2007 (online)

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Abstract

Chemoselective epoxidation of the triple bond of ene-ynamides generates an α-oxocarbene intermediate that effects the intramolecular cyclopropanation of the alkene.

Key words

ynamides - epoxidation - cyclopropanation - oxirene - α-oxocarbene

    References and Notes

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19

For a special issue devoted to the chemistry of ynamides, see: Tetrahedron 2006, 62, issue 16.

22

Representative Procedure: 2-Hydroxy-1-{(1 S *,5 R* )-2-(4-methylbenzenesulfonyl)-2-azabicyclo[3.1.0]hex-1-yl}ethanone (10) To a solution of ynamide 9 (136 mg, 0.486 mmol) in CH2Cl2 (5 mL) at 0 °C were successively added VO(acac)2 (6.4 mg, 0.024 mmol, 0.05 equiv) and TBHP (0.220 mL, 5.5M in decane, 1.21 mmol, 2.5 equiv). After 0.5 h at r.t., the reaction mixture was cooled to 0 °C and cautiously hydrolyzed with a 25% aqueous solution of Na2S2O3. After extraction with CH2Cl2, the combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography (PE-EtOAc, 55:45) to afford 52 mg (40%) of 10 as a colorless oil. IR: 3475, 1701, 1339, 1160, 1086, 903, 808, 666 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.70 (d, J = 8.5 Hz, 2 H), 7.34 (d, J = 8.5 Hz, 2 H), 5.24 (d, AB syst, J = 19.1 Hz, 1 H), 4.56 (d, AB syst, J = 19.1 Hz, 1 H), 3.70 (ddd, J = 10.6, 9.0, 2.5 Hz, 1 H), 3.03 (br s, 1 H, OH), 2.81 (ddd, app td, J = 10.6, 9.5 Hz, 1 H), 2.45 (s, 3 H), 2.27-2.15 (m, 1 H), 1.92-1.83 (m, 3 H), 0.62 (dd, app t, J = 4.5 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 206.3 (s), 144.8 (s), 131.9 (s), 129.7 (d, 2 C), 128.9 (d, 2 C), 67.1 (t), 53.9 (s), 49.6 (t), 34.2 (d), 25.8 (t), 21.6 (q), 16.8 (t). MS (EI, 70 eV): m/z (%) = 295 (4)[M+], 293 (7), 264 (9), 155 (15), 141 (10), 140 (100), 139 (11), 92 (19), 91 (82), 89 (8), 82 (74), 80 (8), 65 (29), 55 (86), 54 (11), 53 (10). Anal. Calcd for C14H17NO4S: C, 56.93; H, 5.80; N, 4.74. Found: C, 56.88; H, 5.93; N, 4.61.