Chemoselective quantum control of carbonyl bonds in Grignard reactions using shaped laser pulses

文献情報

出版日 2010-11-16

DOI 10.1039/C0CP01657H

インパクトファクター 3.676

著者

Caroline Gollub, Markus Kowalewski, Sebastian Thallmair, Regina de Vivie-Riedle

原文を見る

要旨

Grignard reactants like methylmagnesium chloride are not selective with respect to different carbonyl bonds. We present a theoretical study where shaped laser pulses are utilized to prefer specific bonds in a mixture of more than one carbonyl reactant. A mixture of cyclohexanone and cyclopentanone has been chosen as a representative example. The light pulse is supposed to provide the activation energy and to adopt the function of a protecting group. The control aim is to stretch exclusively the C–O bond of one compound to the length required in the Grignard transition state. To guarantee an experimentally realizable bandwidth for the unshaped pulse, we use our recently developed optimal control theory algorithm, which allows the simultaneous optimization of the light field in the time and frequency domain. Highly selective picosecond control pulses could be optimized in the infrared regime suggesting that laser assisted chemoselectivity is possible to a large extent. To obtain control not only on the final product but also on the excitation mechanism, various initial conditions and frequency restrictions were investigated.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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