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Volumn 9, Issue 23, 2007, Pages 4845-4848

Efficient one-pot synthesis of polyfunctionalized thiophenes via an amine-mediated ring opening of EWG-activated 2-methylene-1,3-dithioles

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; DITHIOL DERIVATIVE; DRUG DERIVATIVE; ETHYLAMINE; THIOPHENE DERIVATIVE; TOLUENE;

EID: 36348974670     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol7021752     Document Type: Article
Times cited : (49)

References (54)
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    • (a) Russell, R. K.; Press, J. B. In Comprehensive Heterocyclic Chemistry II; Katritzky, A. R., Rees, C. W., Scriven, E. W. F., Padwa, A., Eds.; Pergamon: New York, 1996; Vol. 2, pp 679-729.
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    • For a representative paper, see: (c) Toru Okazawa, Tetsuya Satoh, Masahiro Miura, Masakatsu Nomura, J. Am. Chem. Soc. 2002, 124, 5286-5287.
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    • For representative reports on the synthesis of substituted thiophenes from open chain precursors, see: a
    • For representative reports on the synthesis of substituted thiophenes from open chain precursors, see: (a) Bartolo, G.; Giuseppe, S.; Alessia, F. Org. Lett. 2000, 2, 351-352.
    • (2000) Org. Lett , vol.2 , pp. 351-352
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    • For reviews on the synthesis and application of α-oxoketene-(S, S)-acetals, see: (a) Dieter, R. K. Tetrahedron 1986, 42, 3029-3096.
    • For reviews on the synthesis and application of α-oxoketene-(S, S)-acetals, see: (a) Dieter, R. K. Tetrahedron 1986, 42, 3029-3096.
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    • Gribble, G. H, Gilchrist, L. T, Eds, Pergamon Press: Oxford, Chapter 1, pp
    • (e) Junjappa, H.; Ila, H.; Mohanta, P. K. In Progress in Heterocyclic Chemistry; Gribble, G. H., Gilchrist, L. T., Eds.; Pergamon Press: Oxford, 2001; Vol. 13, Chapter 1, pp 1-24.
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    • 3 was used as the base, no reaction occurred, with the substrate recovered in almost quantitative yield. When NaOH was used, a few faint spots were detected by TLC, but no desired product was observed.
    • 3 was used as the base, no reaction occurred, with the substrate recovered in almost quantitative yield. When NaOH was used, a few faint spots were detected by TLC, but no desired product was observed.
  • 46
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    • X-ray diffraction data for 2a has been deposited in the Cambridge Crystallographic Data Centre with supplementary publication number of CCDC 634141
    • X-ray diffraction data for 2a has been deposited in the Cambridge Crystallographic Data Centre with supplementary publication number of CCDC 634141. The CIF file is also available in the Supporting Information.
    • The CIF file is also available in the Supporting Information
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    • Based on the fact that more than 2.0 equiv of amine was required to drive the reaction to completion (Table 1, entry 3), it was concluded that the amine substitution may occur prior to the imine hydrolysis.
    • Based on the fact that more than 2.0 equiv of amine was required to drive the reaction to completion (Table 1, entry 3), it was concluded that the amine substitution may occur prior to the imine hydrolysis.
  • 52
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    • For the fragmentation of 1,3-dithiolane, see:, and references therein
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    • For the fragmentation of ketene dithioacetals containing 1,3-dithiolanes, see
    • For the fragmentation of ketene dithioacetals containing 1,3-dithiolanes, see: Samuel, R.; Nair, S. K.; Asokan, C. V. Synlett 2001, 1804-1806.
    • (2001) Synlett , pp. 1804-1806
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    • In all cases, a strong base e.g, sodium hydride, n-butyllithium, lithium diisopropylamide, etc, was used. For an example with a weak base such as aliphatic primary amines, see ref 10, in which the double EWG-activated 1,3-dithiolane moiety was fragmented upon heating to 120°C. For the fragmentation of 1,3-dithioles, see: Ogurtsov, V. A, Rakitin, O. A, Rees, C. W, Smolentsev, A. A, Belyakov, P. A, Golovanov, D. G, Lyssenko, K. A. Org. lett. 2005, 7, 791-794
    • In all cases, a strong base (e.g., sodium hydride, n-butyllithium, lithium diisopropylamide, etc.) was used. For an example with a weak base such as aliphatic primary amines, see ref 10, in which the double EWG-activated 1,3-dithiolane moiety was fragmented upon heating to 120°C. For the fragmentation of 1,3-dithioles, see: Ogurtsov, V. A.; Rakitin, O. A.; Rees, C. W.; Smolentsev, A. A.; Belyakov, P. A.; Golovanov, D. G.; Lyssenko, K. A. Org. lett. 2005, 7, 791-794.


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