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以自然阳光作为可持续能源的对映选择性钯电催化苯胺C-H烯基化反应。

Atropoenantioselective palladaelectro-catalyzed anilide C-H olefinations viable with natural sunlight as sustainable power source.

作者信息

Frey Johanna, Hou Xiaoyan, Ackermann Lutz

机构信息

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen Tammannstraße 237077 Göttingen Germany

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

出版信息

Chem Sci. 2022 Feb 10;13(9):2729-2734. doi: 10.1039/d1sc06135f. eCollection 2022 Mar 2.

DOI:10.1039/d1sc06135f
PMID:35340853
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8890107/
Abstract

Enantioselective electrocatalyzed transformations represent a major challenge. We herein achieved atropoenantioselective pallada-electrocatalyzed C-H olefinations and C-H allylations with high efficacy and enantioselectivity under exceedingly mild reaction conditions. With ()-5-oxoproline as the chiral ligand, activated and non-activated olefins were suitable substrates for the electro-C-H activations. Dual catalysis was devised in terms of electro-C-H olefination, along with catalytic hydrogenation. Challenging enantiomerically-enriched chiral anilide scaffolds were thereby obtained with high levels of enantio-control in the absence of toxic and cost-intensive silver salts. The resource-economy of the transformation was even improved by directly employing renewable solar energy.

摘要

对映选择性电催化转化是一项重大挑战。我们在此实现了在极其温和的反应条件下,以高效和对映选择性进行的阻转对映选择性钯电催化C-H烯基化和C-H烯丙基化反应。以()-5-氧代脯氨酸作为手性配体,活化和未活化的烯烃都是电C-H活化的合适底物。根据电C-H烯基化反应设计了双催化体系,并结合催化氢化反应。由此,在没有有毒且成本高昂的银盐的情况下,以高水平的对映体控制获得了具有挑战性的对映体富集手性酰苯胺支架。通过直接利用可再生太阳能,甚至提高了该转化反应的资源经济性。

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