Mitsunuma Harunobu, Tanabe Shun, Fuse Hiromu, Ohkubo Kei, Kanai Motomu
Graduate School of Pharmaceutical Sciences , The University of Tokyo , 7-3-1 Bunkyo-ku , Tokyo 113-0033 , Japan . Email:
Institute for Advanced Co-Creation Studies , Open and Transdisciplinary Research Initiatives , Osaka University , Osaka 565-0871 , Japan.
Chem Sci. 2019 Jan 17;10(12):3459-3465. doi: 10.1039/c8sc05677c. eCollection 2019 Mar 28.
We describe a hybrid system that realizes cooperativity between an organophotoredox acridinium catalyst and a chiral chromium complex catalyst, thereby enabling unprecedented exploitation of unactivated hydrocarbon alkenes as precursors to chiral allylchromium nucleophiles for asymmetric allylation of aldehydes. The reaction proceeds under visible light irradiation at room temperature, affording the corresponding homoallylic alcohols with a diastereomeric ratio >20/1 and up to 99% ee. The addition of Mg(ClO) markedly enhanced both the reactivity and enantioselectivity.
我们描述了一种混合体系，该体系实现了有机光氧化还原吖啶鎓催化剂与手性铬配合物催化剂之间的协同作用，从而能够以前所未有的方式利用未活化的烃类烯烃作为手性烯丙基铬亲核试剂的前体，用于醛的不对称烯丙基化反应。该反应在室温下可见光照射下进行，得到相应的高烯丙醇，非对映体比例>20/1，对映体过量高达99%。加入Mg(ClO)显著提高了反应活性和对映选择性。
