Process for performing an isolated Pd(II)-mediated oxidation reaction
View Patent ↗There is disclosed a process for performing an isolated Pd(II) mediated oxidation reaction electrochemically. The inventive process is performed on an electrode array device having a plurality of separately addressable electrodes. Preferably, the Pd(II) mediated oxidation is a Wacker reaction. Specifically, there is disclosed a process for conducting an isolated Pd(II) mediated oxidation on a plurality of electrodes, comprising providing an electrode array device having a plurality of electrodes with a conductive electrode surface and a matrix or coating material over the electrodes surfaces; providing a solution bathing the electrode array matrix or coating material and electrode surfaces, wherein the solution comprises a transition metal species and a confining agent; and biasing one or a plurality of electrodes (“selected electrode or electrodes”) with a voltage or current to regenerate the transition metal species required for the isolated Pd(II) mediated oxidation, whereby the confining agent limits diffusion of the transition metal species to a volume surrounding each selected electrode surface.
1. A process for synthesizing site-selective coumarins at known locations of an electrode array device, comprising:
(a) providing an electrode array device with a coating of the region above the electrodes with a porous polymer matrix having free amine groups;
(b) coupling a substituted phenol substrate at selected electrodes of the electrode array device, wherein the substituted phenol substrate is selected from the group consisting of 2-,3-,4-, or 5-substituted amino-phenols, and combinations thereof, wherein the substitution is selected from the group consisting of C 1-6 alkyl, C 1-6 alkoxy, Cl, F, Br, hydroxy, aminoC 1-6 alkyl, and amino; and
(c) performing a site selected Pd(II) catalysed cycloaddition reaction between the phenol substrate and an acetylene at selected electrode sites by providing a solution bathing the electrode array device, wherein the solution comprises a transition metal species and a confining agent, and biasing one or a plurality of selected electrodes on the electrode array device with a voltage or current to regenerate the transition metal species consumed during the cyclooxidation reaction.
2. The process for synthesizing site-selective coumarins at known locations of an electrode array device of claim 1 wherein the porous polymer matrix having free amine groups is selected from the group consisting of amidited agarose, sucrose having oligonucleotide moieties each having an amino-modifier, and combinations thereof.
3. The process for synthesizing site-selective coumarins at known locations of an electrode array device of claim 2 wherein the amino modifier is selected from the group consisting of 5′-3-aminopropyloxy, 2-aminoethoxy, 2(2-aminoethoxy) ethoxy, 2(2(2aminoethoxy)ethoxy)ethoxy, 6-amino, and combinations thereof.
4. A process for site-selective oxidation of alcohols on an electrode array device, comprising:
(a) providing an electrode array device with a coating of at least the region above the electrodes with a porous polyhydroxylated polymer matrix;
(b) performing a site selected oxidation reaction at selected electrode sites by providing a solution bathing the electrode array device, wherein the solution comprises a transition metal species; and
(c) coupling an amine substrate at selected electrodes of the electrode array device to form a bound substrate.
5. The process for site-selective oxidation of alcohols on an electrode array device of claim 4 wherein the oxidation reaction further comprises biasing one or a plurality of selected electrodes on the electrode array device with a voltage or current to regenerate the transition metal species consumed during the oxidation reaction.
6. The process for site-selective oxidation of alcohols on an electrode array device of claim 4 wherein the porous polyhydroxylated polymer matrix is composed of a material selected from the group consisting of agarose, destrose, PEG, dextran, polyvinylalcohol, porous crosslinked polystyrene, poly(2 hydroxyethylacrylate), poly(hydroxylpropylacrylate), and combinations thereof.