Jacobsen's Catalyst for Hydrolytic Kinetic Resolution: Structure Elucidation of Paramagnetic Co(III) Salen Complexes in Solution via Combined NMR and Quantum Chemical Studies

被引：51

作者：

Kemper, Sebastian ^{[2
]}

Hrobarik, Peter ^{[3
]}

Kaupp, Martin ^{[1
]}

Schloerer, Nils E. ^{[2
]}

机构：

[1] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany

[2] Univ Cologne, Dept Chem, D-50939 Cologne, Germany

[3] Slovak Acad Sci, Inst Inorgan Chem, Bratislava 84536, Slovakia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 12期

关键词：

RING-OPENING REACTIONS; EPOXIDATION; EPOXIDES;

D O I：

10.1021/ja806151g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

NMR investigation of chiral Co(III) salen catalysts, important for enantioselective hydrolytic kinetic resolution (HKR), revealed the presence of a paramagnetic high-spin Co(III) species, which is in solvent- and temperature-dependent equilibrium with the known diamagnetic tow-spin Co(III) complex. Combined with quantum chemical DFT calculations, the para- and diamagnetic chemical shifts were used to study the salen ligand conformation of the para- and diamagnetic complexes, resulting in a mechanistic proposal for the enantioselective step in catalysis.

引用

页码：4172 / +

页数：4

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