Kinetic Profiling of Catalytic Organic Reactions as a Mechanistic Tool

被引:239
作者
Blackmond, Donna G. [1 ]
机构
[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
关键词
ASYMMETRIC AUTOCATALYTIC ALKYLATION; ALDOL REACTIONS; ALPHA-SELENENYLATION; REACTION CALORIMETRY; PYRIMIDYL ALDEHYDES; ENANTIOMERIC EXCESS; TERMINAL EPOXIDES; ARYL HALIDES; HYDROGENATION; RATIONALIZATION;
D O I
10.1021/jacs.5b05841
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The use of modern kinetic tools to obtain virtually continuous reaction progress data over the course of a catalytic reaction opens up a vista that provides mechanistic insights into both simple and complex catalytic networks. Reaction profiles offer a rate/concentration scan that tells the story of a batch reaction time course in a qualitative "fingerprinting" manner as well as in quantitative detail. Reaction progress experiments may be mathematically designed to elucidate catalytic rate laws from only a fraction of the number of experiments required in classical kinetic measurements. The information gained from kinetic profiles provides clues to direct further mechanistic analysis by other approaches. Examples from a variety of catalytic reactions spanning two decades of the author's work help to delineate nuances on a central mechanistic theme.
引用
收藏
页码:10852 / 10866
页数:15
相关论文
共 52 条
[1]   New strategies for organic catalysis: The first highly enantioselective organocatalytic Diels-Alder reaction [J].
Ahrendt, KA ;
Borths, CJ ;
MacMillan, DWC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (17) :4243-4244
[2]   Mechanistic Rationalization of Unusual Kinetics in Pd-Catalyzed C-H Olefination [J].
Baxter, Ryan D. ;
Sale, David ;
Engle, Keary M. ;
Yu, Jin-Quan ;
Blackmond, Donna G. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (10) :4600-4606
[3]   Reaction progress kinetic analysis: A powerful methodology for mechanistic studies of complex catalytic reactions [J].
Blackmond, DG .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (28) :4302-4320
[4]   Asymmetric autocatalysis and its implications for the origin of homochirality [J].
Blackmond, DG .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (16) :5732-5736
[5]   Comprehensive kinetic screening of palladium catalysts for Heck reactions [J].
Blackmond, Donna G. ;
Schultz, Thomas ;
Mathew, Jinu S. ;
Loew, Caroline ;
Rosner, Thorsten ;
Pfaltz, Andreas .
SYNLETT, 2006, (18) :3135-3139
[6]   Direct and enantioselective organocatalytic α-chlorination of aldehydes [J].
Brochu, MP ;
Brown, SP ;
MacMillan, DWC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (13) :4108-4109
[7]   Kinetic evidence for a tetrameric transition state in the asymmetric autocatalytic alkylation of pyrimidyl aldehydes [J].
Buono, FG ;
Blackmond, DG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (30) :8978-8979
[8]   Rationalization of an Unusual Solvent-Induced Inversion of Enantio-meric Excess in Organocatalytic Selenylation of Aldehydes [J].
Bures, Jordi ;
Dingwall, Paul ;
Armstrong, Alan ;
Blackmond, Donna G. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (33) :8700-8704
[9]   Correction to Curtin-Hammett Paradigm for Stereocontrol in Organocatalysis by Diarylprolinol Ether Catalysts (vol 134, pg 6741, 2012) [J].
Bures, Jordi ;
Armstrong, Alan ;
Blackmond, Donna G. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (34) :14264-14264
[10]  
Calvin M, 1969, MOL EVOLUTION