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Synlett 2011(17): 2551-2554  
DOI: 10.1055/s-0030-1260333
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Fe(III)-Catalyzed Intermolecular C(sp²)-C(sp³) Dehydration Coupling Reaction of Ketene Dithioacetals and Propargyl Alcohols: Synthesis of Novel gem-Dialkylthiopenten-4-ynes and Further Conversion into Methyl Pent-4-ynoates

Jin-Na Song*a, Zhongxue Fangb, Ying Liub, Ran Lia, Lixin Xua, Badru-Deen Barryb, Qun Liub, Xihe Bib,c, Peiqiu Liao*b
a School of Biological and Agricultural Engineering, Jilin University, Changchun 130022, P. R. of China
Fax: +86(431)85099759; e-Mail: songjn2010@jlu.edu.cn;
b Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. of China
c State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
e-Mail: liaopq774@nenu.edu.cn;
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Publication History

Received 29 June 2011
Publication Date:
27 September 2011 (online)

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Abstract

We report an iron(III)-catalyzed intermolecular C(sp²)-C(sp³) dehydration coupling reaction between ketene dithioacetals and propargyl alcohols, leading to the synthesis of gem-dialkylthiopenten-4-ynes in high efficiency. The products could be transformed into methyl pent-4-ynoates in high yields.

Key words

iron - dehydration - coupling reactions - alkynes - thioacetals

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8

Synthesis of gem-dialkylthiopenten-4-ynes (3); Typical procedure with 3a: To a solution of 1-(1,3-dithiolan-2-ylidene)propan-2-one (1a; 160 mg, 1.0 mmol) and 1,3-diphenylprop-2-yn-1-ol (2a; 250 mg, 1.2 mmol) in MeCN (2.0 mL), FeBr3 (88 mg, 0.3 mmol) was added, and the mixture was stirred at r.t. for 20 min. After completion of the reaction (progress monitored by TLC), the mixture was poured into ice-water and extracted with CH2Cl2 (3 × 15 mL). The combined organic layers were dried with MgSO4, filtered, evaporated in vacuum, and the residue was purified by column chromatography (petroleum ether-diethylether = 10:1) to give product 3a (308 mg, 88% yield) as a white solid. Mp 170-171 ˚C. ¹H NMR (CDCl3, 500 Hz): δ = 2.17 (s, 3 H), 3.63-3.40 (m, 2 H), 3.42-3.45 (m, 2 H), 5.68 (s, 1 H), 7.25-7.31 (m, 1 H), 7.32-7.37 (m, 5 H), 7.49-7.53 (m, 4 H). ¹³C NMR (CDCl3, 125 Hz): δ = 28.4, 35.9, 39.32, 41.9, 85.6, 87.3, 123.1, 124.2, 126.8, 127.0, 128.2, 128.3, 128.6, 131.6, 138.5, 163.8, 194.7. HRMS (ESI-TOF): m/z [M + H]+ calcd for C21H19OS2: 351.0877; found: 351.0833