Nano-to-nano Fe/ppm Pd catalysis of cross-coupling reactions in water

Patent metadata

Field	Value
Publication number	US-10189016-B2
Application number	US-201715624400-A
Country	US
Kind code	B2
Filing date	Jun 15, 2017
Priority date	May 19, 2015
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

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.

First claim

What is claimed is:

1. An aqueous micellar composition in a reaction solvent for enabling cross-coupling reactions containing organometallic nanoparticles (NPs) as catalyst, comprising:
a) an element selected from the group consisting of Fe, C, H, O, Mg, and a halide, or the entire combination thereof; and
b) palladium (Pd), or at least one other metal selected from the group consisting of Pt, Au, Ni, Co, Cu and Mn, or a mixture thereof; wherein the catalyst (NPs) is prepared from a reduction of an iron salt or an iron complex in a solvent and in the presence of a ligand using a reducing agent.

2. The aqueous micellar composition of claim 1 , wherein the iron is selected from the group consisting of a Fe(II) or Fe(III) salt, a Fe(II) salt precursor or Fe(III) salt precursor.

3. The aqueous micellar composition of claim 1 , wherein the Pd is naturally present in the iron salt or the iron complex in amounts less than or equal to 1 ppm, 10 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm or 500 ppm relative to the iron salt or iron complex.

4. The aqueous micellar composition of claim 3 , where the amount of Pd present is controlled by external addition of a palladium salt to an iron salt.

5. The aqueous micellar composition of claim 3 , wherein the reducing reagent is a Grignard reagent selected from the group consisting of MeMgCl, MeMgBr, MeMgI, EtMgCl, EtMgBr, EtMgI, i-PrMgCl, i-PrMgBr, i-PrMgI, PhMgCl, PhMgBr, PhMgI, n-hexyl-MgBr, n-hexyl-MgCl, n-hexyl-MgBr, n-hexyl-MgCl, n-hexyl-MgI, NaBH 4 , liBH 4 , BH 3 -THF, BH 3 —SMe 2 , borane, DIBAL-H and LiAlH 4 ; and mixtures thereof.

6. The aqueous micellar composition of claim 1 further comprising a surfactant, wherein the surfactant is selected from the group consisting of TPGS-500, TPGS-500-M, TPGS-750, TPGS-750-M, TPGS-1000 and TPGS-1000-M, Nok and PTS, or a mixture thereof.

7. The aqueous micellar composition of claim 1 , further comprising a ligand selected from the group consisting of PPh 3 , (o-Tol) 3 P, (p-Tol) 3 P, dppf, dtbpf, BiDime, Tangphos, IMes, IPr, SPhos, t-BuSPhos, XPhos, t-BuXPhos, BrettPhos and t-BuBrettPhos, and HandaPhos or an analog thereof.

8. The aqueous micellar composition of claim 1 , wherein the iron metal complex as nanoparticles is heterogeneous and can be isolated from the composition, stored and recycled.

9. The composition of claim 1 , 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.

Assignees

• Univ California

Inventors

• Lipshutz Bruce H
• Handa Sachin

Classifications

• B01J35/12

  Operations & Transport · mapped topic

• B01J31/22

  Organic complexes · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title

• C07C209/325

  reduction by other means than indicated in C07C209/34 or C07C209/36 · CPC title

• B01J2231/64

  Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations · CPC title