NANO-TO-NANO FE/PPM Pd CATALYSIS OF CROSS-COUPLING REACTIONS IN WATER
AssigneeThe Regents of the University of California
InventorsBruce H. Lipshutz, Sachin Handa
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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.
Claims11
-20. (canceled)
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 BF3K, 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.
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.
The method of claim 11 wherein the source of iron is selected from FeCl3, impure FeCl3 and mixtures thereof, and the reducing agent is a Grignard reagent.
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.
The method of claim 11, wherein the reaction is performed at a range of 20 to 65° C.
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.
Dependencies are inferred from the claim text.