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10475
4. For recent reviews, see: (a) Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56, 8033;
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Eur. J. Org. Chem. 2004, 4741; (d) Enders, D.; Lu¨ttgen, K.; Narine, A. A. Synthesis
2007, 959.
3. Conclusion
We have documented a new catalytic protocol for the thia-Mi-
5. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; John
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Grobel, B.-T.; Seebach, D. Synthesis 1977, 357; (c) Seebach, D. Angew. Chem., Int.
Ed. Engl. 1979, 18, 239; (d) Page, P. C. B.; van Niel, M. B.; Prodger, J. C. Tetrahedron
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9. Carbohydrate Mimics: Concepts and Methods; Chapleur, Y., Ed.; Wiley-VCH:
Weinheim, Germany, 1998; Chapter 6.
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chael addition of
a,b-unsaturated carbonyls, thioacetalization of
aldehydes and ketones, and transthioacetalization of acetals with
high chemoselectivity (aldehyde vs ketone and enone vs ketone)
and diverse functional group (i.e., hydroxy, alkoxy, acyloxy, halide,
amino, nitro, pyrimidyl, acid, and ester) tolerance. In sharp contrast
to those catalyzed by common Brønsted or Lewis acids, the
reactions catalyzed by VO(OTf)2 can be carried out at ambient
temperature with catalyst loading of less than 10 mol % with
straight thiol or dithiol nucleophiles, which augur well for its future
application in organic synthesis.
4. Experimental
4.1. General procedure for thia-Michael addition
To
a
10 mL, round-bottomed flask was placed VO(OTf)2
-unsaturated carbonyl (1.0 mmol) in CH3CN/CH2Cl2
(5 mol %), an
a,b
(1:4, 0.5 M; 1:1, 0.5 M or 1:1, 1.0 M). A given thiol (1.2–2.0 equiv)
was added and the reaction mixture was stirred at ambient tem-
perature for an appropriate reaction time as monitored by TLC (see
Table 1). The resulting reaction mixture was concentrated under
reduced pressure and the residue was purified by column chro-
matography on silica gel to give the corresponding isolated product.
´
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4.2. General procedure for thioacetalization and
transthioacetalization
17. (a) Garg, S. K.; Kumar, R.; Chakraborti, A. K. Tetrahedron Lett. 2005, 46, 1721; (b)
Anand, R. V.; Saravanan, P.; Singh, V. K. Synlett 1999, 415; (c) Besra, R. C.;
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To a 10 mL, round-bottomed flask was placed VO(OTf)2 (5–
15 mol %), a carbonyl or acetal (1.0 mmol) in CH3CN/CH2Cl2 (1:7,
0.25 M or 1:3, 0.17 M). A given dithiol (1.0–2.0 equiv) was added
and the reaction mixture was stirred at ambient temperature for an
appropriate reaction time (see Table 2–4). After the completion of
reaction (as monitored by TLC), the catalyst was filtered off by
a short plug of silica gel. The filtrate was concentrated under
reduced pressure and the residue was purified by column chro-
matography on silica gel to give the corresponding isolated product.
Acknowledgements
22. (a) Zhang, H.; Zhang, Y.; Liu, L.; Xu, H.; Wang, Y. Synthesis 2005, 2129; (b) De, S. K.
Adv. Synth. Catal. 2005, 347, 673.
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5411; (b) Kamal, A.; Chouhan, G. Tetrahedron Lett. 2002, 43, 1347; (c) Karimi, B.;
Ma’mani, L. Synthesis 2003, 2503.
We thank the National Science Council of Taiwan for generous
financial support of this research. Elemental analyses assisted by Dr.
Yih-Tsung Lin and Dr. Jen-Chin Wu (CSIST) are also acknowledged.
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Lipshutz, B. H.; Lee, C.-T.; Servesko, J. M. Org. Lett. 2007, 9, 4713.
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Y.-D.; Chen, C.-T. Org. Lett. 2006, 8, 5633; (c) Chen, C.-T.; Weng, S.-S.; Kao, J.-Q.;
Lin, C.-C.; Jan, M.-D. Org. Lett. 2005, 7, 3343; (d) Chen, C.-T.; Kuo, J.-H.; Ku, C.-H.;
Weng, S.-S.; Liu, C.-Y. J. Org. Chem. 2005, 70, 1328; (e) Chen, C.-T.; Kuo, J.-H.;
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3522; (i) Chen, C.-T.; Lin, J.-S.; Kuo, J.-H.; Weng, S.-S.; Cuo, T.-S.; Lin, Y.-W.;
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Nannestad, T.; Bendix, J. Acta Crystallogr., Sect. C 2007, 63, m51; (b) For a pre-
liminary study by using our VO(OTf)2 in catalyzing thioacetalization of
aldehydes, see: De, S. K. J. Mol. Catal. A: Chem. 2005, 226, 77.
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Supplementary data
Characterization data and 1H, 13C NMR spectra for products 1a0–
4a0 and 5a–34 are provided. Supplementary data associated with
this article can be found in the online version, at doi:10.1016/
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