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瞬态导向基团对映选择性钯催化的C-H活化:便捷合成并苯

Enantioselective Pallada-Electrocatalyzed C-H Activation by Transient Directing Groups: Expedient Access to Helicenes.

作者信息

Dhawa Uttam, Tian Cong, Wdowik Tomasz, Oliveira João C A, Hao Jiping, Ackermann Lutz

机构信息

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.

Wöhler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.

出版信息

Angew Chem Int Ed Engl. 2020 Aug 3;59(32):13451-13457. doi: 10.1002/anie.202003826. Epub 2020 Jun 5.

Abstract

Asymmetric pallada-electrocatalyzed C-H olefinations were achieved through the synergistic cooperation with transient directing groups. The electrochemical, atroposelective C-H activations were realized with high position-, diastereo-, and enantio-control under mild reaction conditions to obtain highly enantiomerically-enriched biaryls and fluorinated N-C axially chiral scaffolds. Our strategy provided expedient access to, among others, novel chiral BINOLs, dicarboxylic acids and helicenes of value to asymmetric catalysis. Mechanistic studies by experiments and computation provided key insights into the catalyst's mode of action.

摘要

通过与瞬态导向基团的协同作用实现了不对称钯催化的C-H烯基化反应。在温和的反应条件下,实现了电化学、阻转选择性C-H活化,具有高位置、非对映和对映选择性控制,以获得高度对映体富集的联芳基和氟化N-C轴手性骨架。我们的策略提供了便捷的途径来获得对不对称催化有价值的新型手性联萘酚、二羧酸和螺旋烯等。通过实验和计算进行的机理研究为催化剂的作用模式提供了关键见解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/33da/7497116/82274836717f/ANIE-59-13451-g005.jpg

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