Discovering Copper for Methane C–H Bond Functionalization

Abstract

The copper complex Tp (CF3)2,Br Cu(NCMe) (1, Tp (CF3)2,Br = hydrotris((3,5-bis(trifluoromethyl)-4-bromo)-pyrazol-1-yl)borate) catalyzes the insertion of the CHCO 2 Et group (from ethyl diazoacetate N 2 CHCO 2 Et, EDA) into the C-H bonds of methane, in a homogeneous process that uses supercritical carbon dioxide (scCO 2 ) as the reaction medium.Other light alkanes such as ethane, propane and butane have been also functionalized with this copper-based catalyst, in the first example of the derivatization of the series of C 1 -C 4 alkanes with this metal with a soluble catalyst.

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

“…We have to mention here Tp X M complexes which were used by Pérez and other authors for alkane functionalization by carbene insertion [195][196][197][198][199][200].…”

Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles

“…[12,13] Foru nactivated hydrocarbon CÀHb onds,t his scale contains [14] the tertiary C À Hbond of tri-p-tolylmethane as the most nucleophilic site (pK a = 32-33). During our studies towards catalytic alkane CÀHb ond functionalizations by carbene insertion from diazo compounds (Scheme 2), [17][18][19][20] we learnt that the metal carbene intermediates involved are reactive enough to enable the ultimate,challenging functionalization of methane.Whenthis method is applied to aseries of alkanes,each CÀHbond leads to ad istinct, isolable product in ad irect manner, with no rearrangement or cleavage processes of the hydrocarbon skeleton being observed. During our studies towards catalytic alkane CÀHb ond functionalizations by carbene insertion from diazo compounds (Scheme 2), [17][18][19][20] we learnt that the metal carbene intermediates involved are reactive enough to enable the ultimate,challenging functionalization of methane.Whenthis method is applied to aseries of alkanes,each CÀHbond leads to ad istinct, isolable product in ad irect manner, with no rearrangement or cleavage processes of the hydrocarbon skeleton being observed.…”

A new magnetic nanoparticle‐supported Schiff base complex of manganese: an efficient and recyclable catalyst for selective oxidation of alcohols

“…Synthesis of manganese catalyst Mn@MNP (6) Complex 3 (0.2 g, 0.55 mmol), CuI (22 mg, 0.11 mmol) and 5 (1 g) were mixed in N,N-dimethylformamide (DMF)-tetrahydrofuran (THF) (1:1, 10 ml) under nitrogen, and N,N-diisopropylethylamine (DIPEA; 2 ml) was added by injection. After stirring at room temperature for three days, the solid was collected using a permanent magnet, then washed with ether (3 × 20 ml), water (3 × 20 ml) and acetone (3 × 20 ml).…”

“…[5] Gava et al developed an efficient copper complex catalyst for C H bond functionalization of methane. [6] Hanhan et al prepared binuclear Pd(II) complex catalysts for Suzuki coupling in water. [7] Meanwhile, there are many transition metal Schiff base complexes, such as Fe, V, [8] Cu, [9] Co, [10] Ag, [11] Pd [12] and Mn, [13] that are widely used in catalytic oxidation of alcohols.…”