Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones

Journal of the American Chemical Society

Volumn 128, Issue 13, 2006, Pages 4481-4486

  Tokunaga, Makoto ^a   Kiyosu, Junya ^a   Obora, Yasushi ^a   Tsuji, Yasushi ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; CARBOXYLIC ACIDS; CATALYSIS; CATALYST SELECTIVITY; COPPER; REACTION KINETICS; SUBSTRATES;

4-ALKYL-2-ARYL-5-OXO-4,5-DIHYDROOXAZOLE-4-CARBOXYLIC ACID ESTERS (AZLACTONES 1); ALCOHOLYSIS; AZLACTONES; FIRST-ORDER REACTION; GRAPHICAL ANALYSIS; KINETIC RESOLUTION; ZEROTH-ORDER REACTION;

ESTERS;

COPPER; LACTONE;

ALCOHOLYSIS; ANALYTIC METHOD; ARTICLE; ASYMMETRIC SYNTHESIS; ENANTIOMER; ENANTIOSELECTIVITY; ESTERIFICATION; KINETICS; QUANTITATIVE ANALYSIS; STOICHIOMETRY;

CATALYSIS; COPPER; KINETICS; LACTONES; OXAZOLES; STEREOISOMERISM;

EID: 33645470534     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja058112j     Document Type: Article

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65. With use of methanol as reagent, 94% ee of 1b and 24% ee of alcoholyzed product were obtained at 22 h (80% convn).
66. rel value, determination of conversion should be performed carefully.1a,d
67. rel values of zeroth- and first-order kinetic resolution were calculated both from theoretical and experimental conversion values using eqs 1, 2, 4, and 5 and are listed as 3 digit numbers.
68. 0) = -kt) for 1b (Table 1, entries 2-5), 1f (entries 12-15), and 1g (entries 16-19) were well fitted below 50% convn (25% convn based on alcohol), 11 (entries 24-27) was moderately fitted, but 1c (entries 6-9) was not fitted (see Supporting Information Figure S-4).