Reaction progress kinetic analysis: a powerful methodology for mechanistic studies of complex catalytic reactions.

Reaction progress kinetic analysis to obtain a comprehensive picture of complex catalytic reaction behavior is described. This methodology employs in situ measurements and simple manipulations to construct a series of graphical rate equations that enable analysis of the reaction to be accomplished from a minimal number of experiments. Such an analysis helps to describe the driving forces of a reaction and may be used to help distinguish between different proposed mechanistic models. This Review describes the procedure for undertaking such analysis for any new reaction under study.

[1]  D. Blackmond,et al.  Rationalization of anomalous nonlinear effects in the alkylation of substituted benzaldehydes. , 2002, Journal of the American Chemical Society.

[2]  D. Burk,et al.  The Determination of Enzyme Dissociation Constants , 1934 .

[3]  A. D. Meijere,et al.  Kleider machen Leute: Heck-Reaktion im neuen Gewand† , 1994 .

[4]  D. Blackmond,et al.  Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides. , 2004, Journal of the American Chemical Society.

[5]  C. Hanes,et al.  Studies on plant amylases: The effect of starch concentration upon the velocity of hydrolysis by the amylase of germinated barley. , 1932, The Biochemical journal.

[6]  J. Skidmore,et al.  Efficient Asymmetric Epoxidation of α,β-Unsaturated Ketones Using a Soluble Triblock Polyethylene Glycol−Polyamino Acid Catalyst , 2001 .

[7]  Sears,et al.  Kinetic investigations of product inhibition in the amino alcohol-catalyzed asymmetric alkylation of benzaldehyde with diethylzinc , 2000, Organic letters.

[8]  D. Blackmond,et al.  Kinetic studies of Heck coupling reactions using palladacycle catalysts: experimental and kinetic modeling of the role of dimer species. , 2001, Journal of the American Chemical Society.

[9]  S. Colonna,et al.  Asymmetric epoxidation of electron-poor olefins-V: Influence on stereoselectivity of the structure of poly-α-aminoacids used as catalysts , 1984 .

[10]  E. Jacobsen,et al.  Practical Considerations in Kinetic Resolution Reactions , 2001 .

[11]  G. C. Fu,et al.  A versatile catalyst for Heck reactions of aryl chlorides and aryl bromides under mild conditions. , 2001, Journal of the American Chemical Society.

[12]  S. Colonna,et al.  Synthetic enzymes—4 , 1983 .

[13]  H. Blaser,et al.  Enantioselective Hydrogenation Using Heterogeneous Modified Catalysts: An Update , 2003 .

[14]  A. Meijere,et al.  Fine Feathers Make Fine Birds: The Heck Reaction in Modern Garb† , 1995 .

[15]  M. Tokunaga,et al.  Asymmetric catalysis with water: efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis. , 1997, Science.

[16]  K. Laidler Rate controlling step: A necessary or useful concept? , 1988 .

[17]  D. Hughes,et al.  Efficient and general protocol for the copper-free sonogashira coupling of aryl bromides at room temperature. , 2003, Organic letters.

[18]  R. Heck Palladium‐Catalyzed Vinylation of Organic Halides , 2005 .

[19]  W. Cabri,et al.  Recent Developments and New Perspectives in the Heck Reaction , 1995 .

[20]  C. Bolm,et al.  Catalytic Enantioselective Conjugate Addition of Dialkylzinc Compounds to Chalcones , 1992 .

[21]  B. Feringa,et al.  Enantioselective conjugate addition of diethylzinc to chalcones catalysed by chiral Ni(II) aminoalcohol complexes , 1994 .