Acceleration of the DABCO-promoted Baylis-Hillman reaction using a recoverable H-bonding organocatalyst

Tetrahedron Letters

Volumn 45, Issue 6, 2004, Pages 1301-1305

  Maher, Declan J ^a   Connon, Stephen J ^a  

^a TRINITY COLLEGE DUBLIN   (Ireland)

Author keywords

Amine; Catalysis; H bonding; Michael addition; Urea

Indexed keywords

1,4 DIAZABICYCLO[2.2.2]OCTANE;

ARTICLE; BAYLIS HILLMAN REACTION; CATALYSIS; CATALYST; COLUMN CHROMATOGRAPHY; HYDROGEN BOND; MICHAEL ADDITION; REACTION ANALYSIS;

EID: 0742322001     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.11.062     Document Type: Article

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55. Surprisingly carbanilide (2) was unsuitable due to poor solubility.
56. As anticipated, ln[PhCHO] versus time plots for all reactions in Table 1 were linear, indicating no significant change in [DABCO] (and hence no significant interaction with 3-7 via H-bonding) over time. All correlation coefficients for the pseudo-first-order rate plots were ≥0.99. A pseudo-second-order treatment of the data gave similar relative rates however given the volatility of methyl acrylate and the long reaction times involved, a pseudo-first-order treatment is preferred here.
57. 16d in terms of greater observed dimerisation constants for aryl thioureas compared to ureas; increased thiourea H-bonding ability seems more important than decreased sulfur (as opposed to oxygen) H-bond accepting ability. This may be significant in the above Baylis-Hillman reactions where catalyst concentrations are high. It should also be noted that the factors influencing the relative ability of ureas and thioureas to bind anions are not fully understood. For an example of superior thiourea binding in a bis(thio)urea system see Ref. 17.
58. 13a has reported inferior aryl thiourea (vs aryl urea) stability at high temperatures (100°C).
59. obs , it does demonstrate the predilection of 4 (as expected from HASB theory) to bind to an oxyanion (once formed) in preference to either benzaldehyde or methyl acrylate.
60. The concept of increased reaction rates through the intermediacy of 9 is attractive, as stabilisation of 1 through sole binding with the urea (as in 8) would increase the equilibrium concentration of the Zwitterion while concurrently decreasing its nucleophilicity.
61. See supplementary material.
62. Ref. [3i] appeared during the preparation of this manuscript.