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锰(I)催化的分散作用促进的C-H/C-C活化

Manganese(I)-Catalyzed Dispersion-Enabled C-H/C-C Activation.

作者信息

Meyer Tjark H, Liu Weiping, Feldt Milica, Wuttke Axel, Mata Ricardo A, Ackermann Lutz

机构信息

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

Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077, Gottingen, Germany.

出版信息

Chemistry. 2017 Apr 24;23(23):5443-5447. doi: 10.1002/chem.201701191. Epub 2017 Apr 3.

DOI:10.1002/chem.201701191
PMID:28317205
Abstract

C-H/C-C Functionalizations were achieved with the aid of a versatile manganese(I) catalyst. Thus, an organometallic manganese-catalyzed C-H activation set the stage for silver-free C-H/C-C transformations with ample substrate scope and excellent levels of chemo-, site-, and diastereo-selectivities. The robust nature of the manganese(I) catalysis regime was reflected by the first C-H/C-C functionalization on amino acids under racemization-free reaction conditions. Detailed experimental and computational mechanistic studies provided strong evidence for a facile C-H activation and a rate-determining C-C cleavage, with considerable contribution from London dispersion interactions.

摘要

借助通用的锰(I)催化剂实现了C-H/C-C官能团化。因此,有机金属锰催化的C-H活化开启了无银C-H/C-C转化的篇章,该转化具有广泛的底物范围以及出色的化学、位点和非对映选择性。锰(I)催化体系的稳健性体现在氨基酸在无消旋化反应条件下的首次C-H/C-C官能团化上。详细的实验和计算机理研究为容易的C-H活化和决速的C-C裂解提供了有力证据,伦敦色散相互作用也有相当大的贡献。

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