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External Reversal of Chirality Transfer in Photoswitches
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-01-18 , DOI: 10.1002/anie.201812284 Christoph Jurissek 1 , Fabian Berger 1 , Fabian Eisenreich 1 , Michael Kathan 1 , Stefan Hecht 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-01-18 , DOI: 10.1002/anie.201812284 Christoph Jurissek 1 , Fabian Berger 1 , Fabian Eisenreich 1 , Michael Kathan 1 , Stefan Hecht 1
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The transfer of stereoinformation is at the heart of asymmetric reactions. By incorporating the natural monoterpene l‐menthone into the backbone of a diarylethene, we achieved efficient chirality transfer upon photocyclization, resulting in the preferred formation of one major closed isomer in a diastereomeric ratio (d.r.) of 85:15. More significantly, we were able to completely reverse the diastereomeric outcome of the ring closure simply by altering the chemical environment or the irradiation conditions. As a result, we could selectively accumulate the less favored minor closed isomer, with remarkable d.r. values of >99:1 and 74:26, respectively. Computations revealed that a stability inversion after photocyclization is the basis for the observed unprecedented control over diastereoselectivity.
中文翻译：
光电开关中手性传递的外部逆转
立体信息的传递是不对称反应的核心。通过将天然单萜l-薄荷酮掺入二芳基乙烯的骨架中，我们在光环化后实现了有效的手性转移，从而导致以85:15的非对映异构体比率（dr）较好地形成了一种主要的封闭异构体。更重要的是，仅通过改变化学环境或辐照条件，我们就能够完全逆转闭环的非对映异构体结果。结果，我们可以有选择地累积不太受欢迎的次要封闭异构体，其dr值分别> 99：1和74:26。计算表明，光环化后的稳定性反转是观察到的对非对映选择性空前控制的基础。
更新日期：2019-01-18
中文翻译：
光电开关中手性传递的外部逆转
立体信息的传递是不对称反应的核心。通过将天然单萜l-薄荷酮掺入二芳基乙烯的骨架中，我们在光环化后实现了有效的手性转移，从而导致以85:15的非对映异构体比率（dr）较好地形成了一种主要的封闭异构体。更重要的是，仅通过改变化学环境或辐照条件，我们就能够完全逆转闭环的非对映异构体结果。结果，我们可以有选择地累积不太受欢迎的次要封闭异构体，其dr值分别> 99：1和74:26。计算表明，光环化后的稳定性反转是观察到的对非对映选择性空前控制的基础。
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