Correlation between pKa and reactivity of quinuclidine-based catalysts in the Baylis-Hillman reaction: Discovery of quinuclidine as optimum catalyst leading to substantial enhancement of scope

Journal of Organic Chemistry

Volumn 68, Issue 3, 2003, Pages 692-700

  Aggarwal, Varinder K ^a   Emme, Ingo ^a   Fulford, Sarah Y ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

BAYLIS-HILLMAN REACTION;

ACETYLATION; ALKALINITY; CATALYSTS; CHEMICAL BONDS; CORRELATION METHODS; SOLVENTS;

CATALYST ACTIVITY;

1,4 DIAZABICYCLO[2.2.2]OCTANE; 3 CHLOROQUINUCLIDINE; 3 QUINUCLIDINOL; ACECLIDINE; ACRYLAMIDE DERIVATIVE; ALDEHYDE DERIVATIVE; AMINE; DIMETHYL SULFOXIDE; ESTER DERIVATIVE; FORMAMIDE; LACTONE DERIVATIVE; METHANOL; QUINUCLIDINE; QUINUCLIDINE DERIVATIVE; QUINUCLIDINONE; SOLVENT; TRIETHANOLAMINE; UNCLASSIFIED DRUG; VINYL DERIVATIVE; WATER;

ALKALINITY; ARTICLE; BAYLIS HILLMAN REACTION; CATALYSIS; CATALYST; CHEMICAL BINDING; CHEMICAL REACTION; CORRELATION ANALYSIS; PKA; REACTION ANALYSIS;

EID: 0037423248     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026671s     Document Type: Article

References (47)

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27. 2O.
28. a relative to 3-acetoxyquinuclidine in protic media. When reactions were conducted in water, 3-acetoxyquinuclidine showed similar rates to DABCO but when the DABCO concentration was halved (to take into account the presence of two nitrogens), the reaction using 3-acetoxyquinuclidine was faster.
29. 1) = 0.6
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31. The use of protic additives to enhance the rates has been described previously although not in the context of autocatalysis; see refs 6c and 12, also: Basaviah, D.; Sarma, P. K. S. Synth Commun. 1990, 20, 1611; Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. Oishi, T.; Oguri, H.; Hirama, M. Tetrahedron: Asymmetry 1995, 6, 1241-1244.
32. The use of protic additives to enhance the rates has been described previously although not in the context of autocatalysis; see refs 6c and 12, also: Basaviah, D.; Sarma, P. K. S. Synth Commun. 1990, 20, 1611; Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. Oishi, T.; Oguri, H.; Hirama, M. Tetrahedron: Asymmetry 1995, 6, 1241-1244.
33. -Propanol and trifluoroethanol were also tested as additives, but they showed less rate enhancement than methanol.
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