Aggregation and Solvation of Chiral N,P-Amide Ligands in Coordinating Solvents: A Computational and NMR Spectroscopic Study

被引：8

作者：

Ronnholm, Petra ^{[1
]}

Lill, Sten O. Nilsson ^{[1
]}

Grafenstein, Jurgen ^{[1
]}

Norrby, Per-Ola ^{[1
]}

Pettersson, Mariell ^{[1
]}

Hilmersson, Goran ^{[1
]}

机构：

[1] Univ Gothenburg, Dept Chem & Mol Biol, S-41296 Gothenburg, Sweden

来源：

CHEMPLUSCHEM | 2012年 / 77卷 / 09期

关键词：

aggregation; density functional calculations; lithium; NMR spectroscopy; N; P ligands; MOLECULAR-ORBITAL METHODS; TRANSITION-METAL-COMPLEXES; GAUSSIAN-TYPE BASIS; ASYMMETRIC ADDITION; LITHIUM AMIDE; AB-INITIO; SUBSTITUTION ENERGIES; DFT METHODS; ENANTIOSELECTIVE ADDITION; CHEMICAL-SHIFTS;

D O I：

10.1002/cplu.201200033

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The lithium amides of a series of chiral N,P ligands were studied in solution. This ligand class had been shown previously to give good selectivities in asymmetric alkylation of benzaldehyde. These lithium amides were found to aggregate into dimers with surprisingly strong coordination of phosphorus to lithium. The equilibrium between dimeric forms was found to depend strongly on non-bonded interactions within the solute and between solute and solvent. Only if dispersion and free-energy contributions were scaled to approximately 20?% of the gas-phase values was it possible to reproduce the experimentally observed aggregation preferences. NMR spectroscopic shieldings were calculated and found to correlate well with the experimentally observed shifts. Calculated Li,P couplings were shown to be a sensitive measure of the Li?P distance.

引用

页码：799 / 806

页数：8

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