Chromophore Activation of α,β-Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions.

Chromophore Activation of α,β-Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions.
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α,β-不饱和羰基化合物的发色团激活及其在对映选择性光化学反应中的应用。

DOI:
10.1002/anie.201804006
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发表时间:
2018-10-26
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Bach T
Bach T
中科院分区:
其他
文献类型:
--
作者:
Brenninger C;Jolliffe JD;Bach T

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正如Theodor von Grothu?和John W.Draper所描述的光化学第一定律指出,只有被辐射物质吸收的光才能影响光化学变化。因此,可以通过使分子的吸收特性与光源的发射相一致来控制分子的光化学行为。具有只吸收短波长光的发色团的化合物不会被长波长的光激发。如果人们可以用化学激活剂可逆地改变化合物的光物理性质,那么就有可能只对被激活的物种进行光激发。对于α,β不饱和的羰基化合物,使用Lewis酸、Brnsted酸或形成相应的亚胺离子可以产生所需的发色团活化,从而在给定的波长下催化光化学反应。在这篇简短的综述中,我们将阐述生色团活化的概念,并讨论它在对映选择性催化中的应用实例。
The first law of photochemistry, as described by Theodor von Grotthuß and John W. Draper, states that only the light absorbed by the irradiated matter can effect photochemical change. Consequently, the photochemical behavior of a molecule can be controlled by bringing its absorbance properties in line with the emission of the light source. A compound with a chromophore that only absorbs light at short wavelengths will not be excited by light of longer wavelengths. If one can reversibly modify the photophysical properties of a compound with a chemical activator, then it is possible to photoexcite only the activated species. For α,β‐unsaturated carbonyl compounds, the use of Lewis acids, Brønsted acids, or the formation of the respective iminium ions can bring about the desired chromophore activation to catalyze a photochemical reaction at a given wavelength. In this Minireview, the concept of chromophore activation will be illustrated, and examples of its implementation in enantioselective catalysis will be discussed.
DOI: 10.1139/v80-282
发表时间: 1980-01-01
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