Piano‐stool Ru (II) arene complexes that contain ethylenediamine and application in alpha‐alkylation reaction of ketones with alcohols

Abstract

A series of piano‐stool Ru (II) complexes (Ru1–7) bearing ethylenediamine with aryl and aliphatic groups were prepared and fully characterized by 1H, 13C, 19F and 31P NMR spectroscopy, FT‐IR and elemental analysis. The crystal structures of Ru2–4 and Ru7 were determined by X‐ray crystallography. They were successfully applied to the alpha(α)‐alkylation of aliphatic and aromatic ketones with alcohols via the borrowing hydrogen strategy in mild reaction conditions within a short time. The catalytic system has a broad substrate scope, which allows the synthesis of alpha alkylated ketones with excellent yields. The electronic and steric effects of complexes on catalytic activity were analysed. The influence of the carbon chain length of the ligand on the alpha‐alkylation reaction of ketones was also investigated. The catalytic cycle was also examined by 1H‐NMR spectroscopy in d8‐toluene.

Cell Death Mechanism of Organometallic Ruthenium(II) and Iridium(III) Arene Complexes on HepG2 and Vero Cells

“…The aromatic p -cymene-C H protons were divided into four different doublets, each with one proton. This is an indication of the formation of a chelate complex, similar to that in our previous studies . Other p -cymene aliphatic protons were observed in the low ppm/high area, as expected.…”

“…The C–N and CC vibrations were observed in the regions of 1000–1250 and 1600 cm –1 , respectively. Additionally, metal–halogen vibrations can be seen in the fingerprint area …”

Recent Advances for Alkylation of Ketones and Secondary Alcohols Using Alcohols in Homogeneous Catalysis

“…At the same year, a series of piano Ru (II) complexes bearing ethylenediamine with N-aryl and N'-alkyl groups were prepared and fully characterized by 1 H, 13 C, 19 F and 31 P NMR spectroscopy, FT-IR and elemental analysis (Scheme 21). [27] The catalytic properties of the complexes were explored in the αalkylation reaction of ketones with alcohols. With RuÀ ethylenediamine as catalyst, the reactions of acetophenone and cyclic ketones, aliphatic ketones with benzyl alcohol and aliphatic alcohols were successfully transformed into the corresponding products in moderate to good yields with selectivity of 56:44-96:4.…”

Iron-Catalyzed Ligand Free α-Alkylation of Methylene Ketones and β-Alkylation of Secondary Alcohols Using Primary Alcohols

“…2,6-Dibenzylcyclohexanone (3zd). 18 Following general procedure A, the title product was obtained as a colorless oil using silica gel column chromatography eluting with 1% ethyl acetate in hexane: yield 48 mg, 35% yield; 1 H NMR (500 MHz, CDCl 3 ) δ 7.35−7.24 (m, 5H), 7.21−7.18 (m, 3H), 7.09 (d,J = 7.5 Hz,2H),2H),2H),2H),2H),2H),2H). 13 C{1H} NMR (125 MHz, CDCl 3 ) δ 216.9, 139.5,129.2,128.3,126.2,53.5,38.4,31.0,28.5.…”