Examination of the Role of Taft-Type Steric Parameters in Asymmetric Catalysis

被引：81

作者：

Sigman, Matthew S. ^{[1
]}

Miller, Jeremie J. ^{[1
]}

机构：

[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 74卷 / 20期

基金：

美国国家科学基金会;

关键词：

NOZAKI-HIYAMA ALLYLATION; TRIDENTATE BIS(OXAZOLINYL)CARBAZOLE LIGAND; HAMMETT SUBSTITUENT CONSTANTS; MONOAMINE-OXIDASE-B; OXAZOLINE LIGANDS; ENANTIOSELECTIVE ADDITION; BIS(OXAZOLINE) LIGANDS; ALLYLIC SUBSTITUTION; DIETHYLZINC ADDITION; CHIRAL LIGANDS;

D O I：

10.1021/jo901698t

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We report the use of Taft steric parameters to correlate the substituent size of a ligand with the enantiomeric ratio of a reaction. Linear free energy relationships can be constructed by plotting the log of enantiomeric ratio(er) versus the steric parameters reported by Taft and modified by Charton. Successful correlations were found for aldehyde and ketone allylation under NHK conditions using modular oxazoline ligands developed in our laboratory. Using these correlations, ligands were designed and evaluated for carbonyl allylation reactions. A break in the Charton plot results and is attributed to a global structural change in the catalyst. Additionally, several previously reported enantioselective reactions are analyzed resulting in excellent correlations for both catalysts and substrates. Finally, limitations and issues are presented with illustrative examples.

引用

页码：7633 / 7643

页数：11

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