Reevaluation of the mechanism of the Baylis-Hillman reaction: Implications for asymmetric catalysis

Angewandte Chemie - International Edition

Volumn 44, Issue 11, 2005, Pages 1706-1708

  Aggarwal, Varinder K ^a   Fulford, Sarah Y ^a   Lloyd Jones, Guy C ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

Asymmetric catalysis; Autocatalysis; Kinetics; Proton transfer; Reaction mechanisms

Indexed keywords

ALCOHOLS; AMINES; CATALYSIS; CATALYSTS; CHARGE TRANSFER; CHEMICAL BONDS; PROTONS; RATE CONSTANTS;

ASYMMETRIC CATALYSIS; BAYLIS-HILLMAN REACTION; PROTON TRANSFER; RATE-LIMITING STEP (RLS);

REACTION KINETICS;

EID: 17044437071     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200462462     Document Type: Article

References (28)

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17. The reactions display a noticeable contraction in volume as they proceed. However, the nonlinear relationship between the conversion and the concentrations of all components is not the origin of the induction period. See Supporting Information for a full discussion.
18. The kinetics were simulated using MacKinetics (Leipold Associates, USA); see Supporting Information for full discussion.
19. d-1 observed in the later phase of the reaction when significant 6/d-O-6 has accumulated.
20. The question remains as to what mediates step 3 in the absence of significant quantities of product. The possibility that a second molecule of quinuclidine acts as a base was eliminated by a study of the effect of doubling the catalyst loading which caused only an approximately 1.75-fold increase in rate in the crucial early stages of reaction - exactly as would be predicted on the basis of first-order dependency on each of the three reaction components when the dilution of aldehyde and alkene caused by increased catalyst loading is taken into account. We therefore suggest that traces of protic species, for example, water, enol, etc., may well be sufficient to initiate reaction. A hemiacetal anion intermediate (derived from 5 and 4) has been proposed by McQuade and co-workers to effect proton transfer. See Reference [14].
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27. Such a model to account for asymmetric induction has been suggested by Hatakeyama, see Reference [12a].
28. Note added in proof: McQuade and co-workers have independently found a substantial kinetic isotope effect during the initial phase of the Baylis-Hillman reaction (< 10% conversion). See: K. E. Price, S. J. Broadwater, H. M. Jung, D. T. McQuade, Org. Lett. 2005, 147-150.