NANO-TO-NANO FE/PPM Pd CATALYSIS OF CROSS-COUPLING REACTIONS IN WATER

Abstract

In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt.

What is claimed is: 
     
         1 .- 20 . (canceled) 
     
     
         21 . A method for performing a cross coupling reaction between a first coupling substrate of the formula I with a second coupling substrate of the formula II in a reaction condition sufficient to form the coupled product of the formula III: 
       
         
           
           
               
               
           
         
         wherein:
 X is selected from the group consisting of Cl, Br and I, and pseudo halides; 
 Y is selected from the group consisting of B(OH) 2 , B(OR) 2 , cyclic boronates, acyclic boronates, B(MIDA), Bpin and BF 3 K, where R is selected from methyl, ethyl, propyl, butyl, isopropyl, ethylene glycol, trimethylene glycol and pinacol; 
 each of the groups 
 
       
       
         
           
           
               
               
           
         
       
       is independently selected from the group consisting of an alkene or a substituted alkene, a cycloalkene or a substituted cycloalkene, an alkyne or a substituted alkyne, an aryl or a substituted aryl, and a heteroaryl or a substituted heteroaryl;
 the method comprising: 
 i) forming a micelle composition comprising aqueous nanoparticles in which the partners I and II are solubilized in water, and an organometallic complex comprising iron nanoparticles, wherein another metal is present in less than 50,000 ppm relative to the limiting substrate of the formula I or formula II; and 
 ii) contacting the first coupling substrate with the second coupling substrate in water under a condition sufficient to form a product mixture comprising a cross coupling product of the formula III. 
 
     
     
         22 . The method of  claim 21 , wherein the metal, other than Pd, is selected from the group consisting of Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or a mixture thereof. 
     
     
         23 . The method of  claim 22  further comprising:
 iii) contacting the product mixture with an organic solvent to form an organic phase and an aqueous phase; and 
 iv) separating the organic phase from the aqueous phase containing the micelle composition as well as the iron/ppm Pd nanoparticles. 
 
     
     
         24 . The method of  claim 23  further comprising:
 v) re-cycling the aqueous phase containing the micelle composition and Fe/ppm Pd nanoparticles for use in a subsequent cross coupling or other reactions. 
 
     
     
         25 . The method of  claim 21 , wherein the reaction solvent is water, and the reaction solvent further comprising an organic solvent, wherein the organic co-solvent is present in at least 5%, 10%, 20%, 30%, 40%, 50%, 70%, 80% or at least 90% wt/wt. 
     
     
         26 . The method of claim  11 , wherein the organic co-solvent is present at a wt of organic co-solvent to the wt of water (wt/wt) of 1/10, 2/10, 5/10, 10/10, 20/10, 30/10, 50/10, 70/10, 90/10, 100/10, 200/10, 300/10, 500/10, 700/10, 900/10, 1,000/10, 5,000/10 or 10,000/10. 
     
     
         27 . The method of claim  11  wherein the source of iron is selected from FeCl 3 , impure FeCl 3  and mixtures thereof, and the reducing agent is a Grignard reagent. 
     
     
         28 . The method of claim  11 , wherein the reaction condition is a Suzuki-Miyaura coupling condition or a Sonogashira coupling condition, or other common Pd-catalyzed cross-coupling reactions. 
     
     
         29 . The method of claim  11 , wherein the reaction is performed at a range of 20 to 65° C. 
     
     
         30 . The method of claim  11 , further comprising removal of the organic solvent in vacuo, and further isolating the nanoparticles from the reaction mixture for re-use or recycling.