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Synlett 2004(1): 85-88  
DOI: 10.1055/s-2003-43377
LETTER
© Georg Thieme Verlag Stuttgart · New York

Reaction of PhSeCl or PhSCl with 2,3-Allenoic Acids: An Efficient Synthesis of β-Organoselenium or β-Organosulfur Substituted Butenolides

Shengming Ma*a,b, Feng Pana, Xueshi Haoa, Xian Huanga
a Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, P. R. China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China
Fax: +86(21)64167510; e-Mail: masm@mail.sioc.ac.cn;
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Publication History

Received 1 September 2003
Publication Date:
04 December 2003 (online)

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Abstract

β-Organoselenium or β-organosulfur-substituted butenolides were prepared via the electrophilic cyclization of 2,3-allenoic acids with PhSeCl or PhSCl.

Key words

allenes - carboxylic acids - electrophilic cyclizations - selenium - sulfur - lactones

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Typical Procedure for the Synthesis of 5-butyl-4-phenylselanyl-5 H -furan-2-one (2a): To a solution of 1a (41 mg, 0.3 mmol) in MeCN (1.5 mL) in a dry Schlenk tube was added PhSeCl (86 mg, 0.45 mmol) in MeCN (1.5 mL) at 0 °C under N2 atmosphere. After the reaction was complete as monitored by TLC (eluent: petroleum ether-EtOAc, 8:1), the reaction mixture was evaporated and purified by flash chromatography on silica gel to give 2a (79 mg, 91%) as a liquid. IR(neat): 1748, 1571 cm-1. 1H NMR (CDCl3, 300 MHz): δ = 7.68-7.60 (m, 2 H), 7.50-7.34 (m, 3 H), 5.46 (d, J = 1.5 Hz, 1 H), 5.04 (ddd, J 1 = 1.5 Hz, J 2 = 3.5 Hz, J 3 = 7.7 Hz, 1 H), 1.98-1.85 (m, 1 H), 1.73-1.54 (m, 1 H), 1.53-1.23 (m, 4 H), 0.90 (t, J = 7.4 Hz, 3 H). 13C NMR (CDCl3, 75.4 MHz): δ = 171.1, 169.7, 135.9, 130.2, 130.1, 124.5, 115.9, 84.2, 33.7, 26.00, 22.3, 13.8. MS (70 eV): m/z (%) = 296 (73.33) [M + (80Se)], 239(100). Anal. Calcd for C14H16O2Se: C, 56.97; H, 5.46. Found: C, 57.21; H, 5.70. All other new products were characterized similarly.