Delcourt Marie-Léonie, Felder Simon, Turcaud Serge, Pollok Corina H, Merten Christian, Micouin Laurent, Benedetti Erica
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques-UMR8601 CNRS, Université Paris Descartes, Sorbonne Paris Cité, UFR Biomédicale , 45 rue des Saints Pères , 75006 Paris , France.
Fakultät für Chemie und Biochemie, Lehrstuhl für Organische Chemie 2 , Ruhr-Universität Bochum , Universitätsstraße , 150 44801 Bochum , Germany.
J Org Chem. 2019 May 3;84(9):5369-5382. doi: 10.1021/acs.joc.9b00372. Epub 2019 Mar 28.
We report herein a general, practical method based on asymmetric transfer hydrogenation (ATH) to control the planar chirality of a range of substituted [2.2]paracyclophanes (pCps). Our strategy enabled us to perform both the kinetic resolution (KR) of racemic compounds and the desymmetrization of centrosymmetric meso derivatives on synthetically useful scales. High selectivities (up to 99% ee) and good yields (up to 48% for the KRs and 74% for the desymmetrization reactions) could be observed for several poly-substituted paracyclophanes, including a series of bromine-containing molecules. The optimized processes could be run up to the gram scale without any loss in the reaction efficiencies. Because of its broad applicability, the ATH approach appears to be the method of choice to access planar chiral pCps in their enantiopure form.
我们在此报告一种基于不对称转移氢化（ATH）的通用实用方法，用于控制一系列取代的[2.2]对环芳烷（pCps）的平面手性。我们的策略使我们能够在合成有用的规模上对外消旋化合物进行动力学拆分（KR）以及对中心对称的内消旋衍生物进行去对称化。对于几种多取代的对环芳烷，包括一系列含溴分子，可以观察到高选择性（高达99% ee）和良好的产率（KR高达48%，去对称化反应高达74%）。优化后的工艺可以扩大到克级规模，而不会有任何反应效率的损失。由于其广泛的适用性，ATH方法似乎是获得对映体纯形式的平面手性pCps的首选方法。
