Issue 6, 2021

Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

Abstract

Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80–100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N–H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.

Graphical abstract: Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

Supplementary files

Article information

Article type
Paper
Submitted
30 nov 2020
Accepted
22 dec 2020
First published
22 dec 2020

Dalton Trans., 2021,50, 2023-2031

Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

L. P. Cailler, A. P. Kroitor, A. G. Martynov, Y. G. Gorbunova and A. B. Sorokin, Dalton Trans., 2021, 50, 2023 DOI: 10.1039/D0DT04090H

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