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镍催化吲哚与未活化氯代烷烃的C-H烷基化反应：Ni(i)/Ni(iii)途径的证据

Nickel-catalyzed C-H alkylation of indoles with unactivated alkyl chlorides: evidence of a Ni(i)/Ni(iii) pathway.

作者信息

Pandey Dilip K, Ankade Shidheshwar B, Ali Abad, Vinod C P, Punji Benudhar

机构信息

Organometallic Synthesis and Catalysis Group , Chemical Engineering Division , CSIR-National Chemical Laboratory (CSIR-NCL) , Dr. Homi Bhabha Road , Pune 411 008 , Maharashtra , India . Email:

Academy of Scientific and Innovative Research (AcSIR) , CSIR-NCL , Dr. Homi Bhabha Road , Pune , India.

出版信息

Chem Sci. 2019 Aug 19;10(41):9493-9500. doi: 10.1039/c9sc01446b. eCollection 2019 Nov 7.

DOI:10.1039/c9sc01446b
PMID:32110305
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7017866/
Abstract

A mild and efficient nickel-catalyzed method for the coupling of unactivated primary and secondary alkyl chlorides with the C-H bond of indoles and pyrroles is described which demonstrates a high level of chemo and regioselectivity. The reaction tolerates numerous functionalities, such as halide, alkenyl, alkynyl, ether, thioether, furanyl, pyrrolyl, indolyl and carbazolyl groups including acyclic and cyclic alkyls under the reaction conditions. Mechanistic investigation highlights that the alkylation proceeds through a single-electron transfer (SET) process with Ni(i)-species being the active catalyst. Overall, the alkylation follows a Ni(i)/Ni(iii) pathway involving the rate-influencing two-step single-electron oxidative addition of alkyl chlorides.

摘要

本文描述了一种温和且高效的镍催化方法，用于未活化的伯烷基和仲烷基氯与吲哚和吡咯的C-H键的偶联反应，该反应具有高度的化学选择性和区域选择性。该反应在反应条件下能够耐受多种官能团，如卤化物、烯基、炔基、醚、硫醚、呋喃基、吡咯基、吲哚基和咔唑基，包括无环和环状烷基。机理研究表明，烷基化反应通过单电子转移（SET）过程进行，活性催化剂为Ni(i)物种。总体而言，烷基化反应遵循Ni(i)/Ni(iii)途径，涉及影响反应速率的烷基氯的两步单电子氧化加成。

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