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质子离子液体作为试剂、催化剂和溶剂：硫氰酸1-甲基咪唑鎓

Protic Ionic Liquid as Reagent, Catalyst, and Solvent: 1-Methylimidazolium Thiocyanate.

作者信息

Andreev Ivan A, Ratmanova Nina K, Augustin André U, Ivanova Olga A, Levina Irina I, Khrustalev Victor N, Werz Daniel B, Trushkov Igor V

机构信息

Dmitry Rogachev National Medical Research Center of Pediatric Hematology, Oncology and Immunology, Samory Mashela 1, 117997, Moscow, Russian Federation.

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, 119991, Moscow, Russian Federation.

出版信息

Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7927-7934. doi: 10.1002/anie.202016593. Epub 2021 Feb 26.

DOI:10.1002/anie.202016593
PMID:33433034
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8048580/
Abstract

We propose a new concept of the triple role of protic ionic liquids with nucleophilic anions: a) a regenerable solvent, b) a Brønsted acid inducing diverse transformations via general acid catalysis, and c) a source of a nucleophile. The efficiency of this strategy was demonstrated using thiocyanate-based protic ionic liquids for the ring-opening of donor-acceptor cyclopropanes. A wide variety of activated cyclopropanes were found to react with 1-methylimidazolium thiocyanate under mild metal-free conditions via unusual nitrogen attack of the ambident thiocyanate ion on the electrophilic center of the three-membered ring affording pyrrolidine-2-thiones bearing donor and acceptor substituents at the C(5) and C(3) atoms, respectively, in a single time-efficient step. The ability of 1-methylimidazolium thiocyanate to serve as a triplex reagent was exemplarily illustrated by (4+2)-annulation with 1-acyl-2-(2-hydroxyphenyl)cyclopropane, epoxide ring-opening and other organic transformations.

摘要

我们提出了一种关于具有亲核阴离子的质子离子液体三重作用的新概念

a）可再生溶剂，b）通过广义酸催化引发多种转化的布朗斯特酸，以及c）亲核试剂来源。使用基于硫氰酸盐的质子离子液体进行供体-受体环丙烷的开环反应，证明了该策略的有效性。发现多种活化的环丙烷在温和的无金属条件下与硫氰酸1-甲基咪唑鎓反应，通过亲核性硫氰酸根离子对三元环亲电中心的异常氮原子进攻，在一个高效的步骤中分别在C(5)和C(3)原子上得到带有供体和受体取代基的吡咯烷-2-硫酮。硫氰酸1-甲基咪唑鎓作为三重试剂的能力通过与1-酰基-2-(2-羟基苯基)环丙烷的(4+2)环化、环氧开环及其他有机转化得到了例证。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de28/8048580/90b25d1aeeef/ANIE-60-7927-g006.jpg
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2
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3
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Int J Mol Sci. 2021 May 21;22(11):5430. doi: 10.3390/ijms22115430.
Org Lett. 2020 Nov 20;22(22):9016-9021. doi: 10.1021/acs.orglett.0c03413. Epub 2020 Nov 10.
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