Phosphine-catalyzed hydration and hydroalkoxylation of activated olefins: Use of a strong nucleophile to generate a strong base

Journal of the American Chemical Society

Volumn 125, Issue 29, 2003, Pages 8696-8697

  Stewart, Ian C ^a   Bergman, Robert G ^a   Toste, F Dean ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; KETONE; PHOSPHINE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; HYDRATION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; SYNTHESIS;

EID: 0038637120     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035232n     Document Type: Article

References (24)

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6. Use of high pressure for olefin hydration: Jenner, G. Tetrahedron Lett. 2001, 42, 4807-4810. Jenner, G. Tetrahedron 2002, 58, 4311-4317.
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11. 3 was added via vacuum -transfer. The flask was sealed and left for the time indicated. The reaction mixture was then filtered through a pad of silica and concentrated under reduced pressure. In the case of methanol addition the desired product was obtained in high purity without chromatography. All other reactions required flash column chromatography using mixtures of hexanes and ethyl acetate as the eluent to afford pure product.
12. DFT calculations suggest that hydration of 4-phenyl-3-buten-2-one is less enthalpically favored.
13. For another example of this, see: Allen, A. A.; Duffner, R.; Kurzer, F. Tetrahedron 1978, 34, 1247-1250.
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16. 3 from the β-phosphonium ketone. Displacements of this type, however, are extremely rare.
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21. This observation is also consistent with 5 being the resting state; however, the 5→4 proton transfer should be exothermic and rapid.
22. A catalytic amount of enone is likely formed from elimination of methanol from 2-methoxy-4-hexanone. The mechanism of the elimination is not necessarily the microscopic reverse of the mechanism for the addition reactions described in Scheme 1.
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