Pentacoordinate organosilicate-catalyzed Michael addition of β-keto esters to 3-buten-2-one

European Journal of Organic Chemistry

Volumn , Issue 8, 2001, Pages 1445-1448

  Tateiwa, Jun Ichi ^a   Hosomi, Akira ^a  

^a UNIVERSITY OF TSUKUBA   (Japan)

Author keywords

Catalysts; Hypervalent compounds; Michael addition; Silicates

Indexed keywords

ESTER DERIVATIVE; ORGANOSILICON DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ORGANIC CHEMISTRY;

EID: 0035044525     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200104)2001:8<1445::AID-EJOC1445>3.0.CO;2-Q     Document Type: Article

References (22)

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2. For recent reviews on organic chemistry with organosilicon compounds see, for example: M. A. Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, Wiley, New York, 2000.
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9. D. F. Evans, A. M. Z. Slawin, D. J. Williams, C. Y. Wong, J. D. Woollins, J. Chem. Soc., Dalton Trans. 1992, 2383-2387. For the preparation of 1a we employed potassium tert-butoxide instead of potassium metal. Thus, the silicate 1a was prepared with trimethoxyphenylsilane, catechol, potassium tert-butoxide, and ethanol at ambient temperature. The silicate 1b was prepared with trimethoxyphenylsilane, catechol, and triethylamine at ambient temperature. Triethylamine was used as the reactant as well as the solvent.
10. U. Dettlaff-Weglikowska, E. Hey-Hawkins, H. G. von Schnering, Z. Naturforsch., B: Chem. Sci. 1991, 46, 609-614.
11. 3) was added to the mixture which was then filtered to remove the resulting precipitate. The filtrate was concentrated and the residue was subjected to column chromatography on silica gel [eluents: hexane and hexane/ethyl acetate (v/v = 9:1)] to furnish the 1,4-adduct 3a as a colorless oil (229.5 mg, 0.96 mmol, 96%). A minimum amount of chloroform was added for smooth stirring of the reaction mixture.
12. See, for example: [9a] E. Keller, B. L. Feringa, Tetrahedron Lett. 1996, 37, 1879-1882.
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14. [9c] E. Keller, B. L. Feringa, Synlett 1997, 842-844. Ytterbium triflate in combination with water or silica gel catalyzes the Michael addition of a β-keto ester to an α,β-unsaturated ketone.
15. The silicate 6 was similarly prepared from triethoxysilane or tetramethoxysilane, catechol, and triethylamine at room temperature.
16. M. E. Jung, in Comprehensive Organic Synthesis (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford, 1991, vol. 4, chapter 1.1, p. 1-67.
17. A mixture of tetraalkoxysilane and cesium fluoride is known to promote stoichiometrically the Michael addition of an alkyl ketone to an α,β-unsaturated ketone.
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20. 1H NMR spectroscopy (150.8 mg, 0.97 mmol, 97%, 2b:2b-d = 70:30).
21. Multi-functional lanthanide catalysts providing a Bronsted base site as well as a Lewis acid site. See, for example: [14a] H. Sasai, T. Arai, Y. Satow, K. N. Houk, M. Shibasaki, J. Am. Chem. Soc. 1995, 117, 6194-6198.
22. [14b] H. Sasai, E. Emori, T. Arai, M. Shibasaki, Tetrahedron Lett. 1996, 37, 5561-5564.