Process for performing an isolated Pd(0) catalyzed reaction electrochemically on an electrode array device

Abstract

There is disclosed a process for performing an isolated Pd(0) catalyzed reaction electrochemically on an electrode array device. Preferably the Pd(0) catalyzed reaction is a Heck reaction. Specifically, there is disclosed a process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes, comprising providing an electrode array device having a matrix or coating material over metallic or conductive electrodes surfaces and a plurality of electrodes; providing a solution bathing the electrode array device, wherein the solution comprises a transition metal catalyst and a confining agent; and biasing one or a plurality of electrodes on the electrode array device with a voltage or current to regenerate the transition metal catalyst required for the isolated Pd(0) catalyzed reaction, whereby the confining agent limits diffusion of the transition metal catalyst to a volume surrounding each selected electrode surface.

1 . A process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes, comprising: 
 (a) providing an electrode array device having a matrix or coating material over metallic or conductive electrodes surfaces and a plurality of electrodes;    (b) providing a solution bathing the electrode array device, wherein the solution comprises a transition metal catalyst, and a confining agent;    (c) biasing one or a plurality of electrodes on the electrode array device with a voltage or current to regenerate the transition metal catalyst consumed during the Pd(0) catalyzed reaction, whereby the confining agent limits diffusion of the transition metal catalyst to a volume surrounding each selected electrode surface.    
     
     
         2 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 1  wherein the isolated Pd(0) catalyzed reaction is selected from the group consisting of a Heck reaction, a Suzuki coupling reaction, displacement of an aryl halide with an RS-nucleophile of NH 2 R nucleophile, coupling an aryl bromide to an aluminoacetylene Al (C≡C—R) 4  Na salt, displacement of an aryl halide with an esterenolate, alkyl group Suzuki coupling (aryl boron reagent with alkyl halide), Stille coupling R—X plus R′SnR″ 3 , alkyne-BF 3  salt coupling to aryl triflate halide, vinyl-BF 3  salt or alkyne-BF 3  salt coupling, reaction of an alcohol with alkyl/allyl carbonate to make alcohol allyl ether, conversion of an alpha aminoacetylene to a ketene, conversion of Ar—X plus acid chloride to acetylinic ketone, and combinations thereof.  
     
     
         3 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 2  wherein the transition metal catalyst for an isolated Pd(0) catalyzed reaction is a palladium (Pd) or a platinum (Pt) catalyst system.  
     
     
         4 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 3  wherein a Pd catalyst is stabilized with stabilizer selected from the group consisting of a phosphine ligand, a phosphite ligand, an arsenic derivative, a triphenylphosphine ligand, and combinations thereof.  
     
     
         5 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 4  wherein the Pd catalyst is stabilized by a triphenylphosphine ligand.  
     
     
         6 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 1  wherein the confining agent is an oxidant added to solution sufficient to convert Pd(0) back to Pd(II).  
     
     
         7 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 6  wherein the confining agent is an oxidant selected from the group consisting of substituted or unsubstituted allyl alkyl carbonates, allyl acetate, O 2 , peroxides, quinines, and combinations thereof.  
     
     
         8 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 6  wherein the confining agent is a substituted or unsubstituted allyl alkyl carbonate wherein the alkyl moiety can be a C 1-6  alkyl group.  
     
     
         9 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 1  wherein the biasing step used a voltage no greater than 2.4 V.  
     
     
         10 . The process for conducting an isolated Pd(0) catalyzed reaction on a plurality of electrodes of  claim 1  wherein the biasing step was performed for a time of from about 1 sec to 3 min.