RSS-Feed abonnieren
DOI: 10.1055/s-0030-1260333
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
Publikationsverlauf
Publikationsdatum:
27. September 2011 (online)
![](https://www.thieme-connect.de/media/synlett/201117/lookinside/thumbnails/10.1055-s-0030-1260333-1.jpg)
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
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Shi W.Liu C.Lei AW. Chem. Soc. Rev. 2011, 40: 2761 -
1b
Metal-Catalyzed Cross-Coupling
Reactions
2nd Ed.:
de Meijere A.Diederich F. Wiley-VCH; Weinheim: 2004. - For reviews, see:
-
2a
Pan L.Liu Q. Synlett 2011, 1073 -
2b
Dieter RK. Tetrahedron 1986, 42: 3029 -
2c
Junjappa H.Ila H.Asokan CV. Tetrahedron 1990, 46: 5423 - Selected examples, see:
-
3a
Bi X.Dong D.Liu Q.Pan W.Zhao L.Li B. J. Am. Chem. Soc. 2005, 127: 4578 -
3b
Dong D.Bi X.Liu Q.Cong F. Chem. Commun. (Cambridge) 2005, 28: 3580 -
3c
Bi X.Zhang J.Liu Q.Tan J.Li B. Adv. Synth. Catal. 2007, 349: 2301 -
3d
Bi X.Dong D.Li Y.Liu Q.Zhang Q. J. Org. Chem. 2005, 70: 10886 - 4
Liang D.Wang M.Bekturhun B.Xiong B.Liu Q. Adv. Synth. Catal. 2010, 352: 1593 -
5a
Zhu G.Negishi E.-i. Chem. Eur. J. 2008, 14: 311 -
5b
Dulcere JP.Tawil M.Santelli M. J. Org. Chem. 1990, 55: 571 -
5c
Rosiak A.Müller RM.Christoffers J. Monatsh. Chem. 2007, 138: 13 - For reviews on iron-catalyzed reactions, see:
-
6a
Iron Catalysis
in Organic Chemistry: Reactions and Applications
Plietker B. Wiley-VCH; Weinheim: 2008. -
6b
Sun C.-L.Li B.-J.Shi Z.-J. Chem. Rev. 2010, 111: 1293 -
6c
Bolm C.Legros J.Le Paih J.Zani L. Chem. Rev. 2004, 104: 6217 -
7a
Wang Y.Li W.-Q.Che G.Bi X.Liao P.Zhang Q.Liu Q. Chem. Commun. (Cambridge) 2010, 46: 6843 -
7b
Wang Y.Bi X.Li D.Liao P.Wang Y.Yang J.Zhang Q.Liu Q. Chem. Commun. (Cambridge) 2011, 47: 809 -
7c
Wang Y.Bi X.Li W.-Q.Li D.Zhang Q.Liu Q.Ondon BS. Org. Lett. 2011, 13: 1722 -
9a
Dong D.Ouyang Y.Yu H.Liu Q.Liu J.Wang M.Zhu J. J. Org. Chem. 2005, 70: 4535 -
9b
Liu Q.Che G.Yu H.Liu Y.Zhang J.Zhang Q.Dong D. J. Org. Chem. 2003, 68: 9148 -
9c
Ouyang Y.Dong D.Zheng C.Yu H.Liu Q.Fu Z. Synthesis 2006, 3801 -
9d
Yu H.Liu Q.Yin Y.Fang Q.Zhang J.Dong D. Synlett 2004, 999 -
10a
Tosh DK.Chinn M.Ivanov AA.Klutz AM.Gao Z.-G.Jacobson KA. J. Med. Chem. 2009, 52: 7580 -
10b
Prasad JVNV.Boyer FE.Chupak L.Dermyer M.Ding Q.Gavardinas K.Hagen SE.Huband MD.Jiao W.Kaneko T.Maiti SN.Melnick M.Romero K.Patterson M.Wu X. Bioorg. Med. Chem. Lett. 2006, 16: 5392 -
10c
Wulff WD.McCallum JS.Kunng FA.
J. Am. Chem. Soc. 1988, 110: 7419 -
10d
Spinella A.Caruso T.Martino M.Sessa C. Synlett 2001, 1971 - For examples on the ring-opening reactions of 1,3-dithiane-containing α-oxo ketene dithioacetals under acidic conditions, see:
-
11a
Liu Q.Che G.Yu H.Liu Y.Zhang J.Zhang Q.Dong D. J. Org. Chem. 2003, 68: 9148 -
11b
Dong D.Ouyang Y.Yu H.Liu Q.Liu J.Wang M.Zhu J. J. Org. Chem. 2005, 70: 4535
References
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