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

Patent metadata

Field	Value
Publication number	US-2017341069-A1
Application number	US-201715624400-A
Country	US
Kind code	A1
Filing date	Jun 15, 2017
Priority date	May 19, 2015
Publication date	Nov 30, 2017
Grant date	—

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 .- 20 . (canceled)

21 . 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.

22 . The aqueous micellar composition of claim 22 , 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.

23 . The aqueous micellar composition of claim 21 , 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.

24 . The aqueous micellar composition of claim 23 , where the amount of Pd present is controlled by external addition of a palladium salt to an iron salt.

25 . The aqueous micellar composition of claim 23 , 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.

26 . The aqueous micellar composition of claim 1 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.

27 . 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.

28 . 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.

29 . 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.

30 . 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 as a reaction solvent, 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.

31 . The method of claim 11 , 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.

32 . The method of claim 30 , 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.

33 . The method of claim 32 , 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.

34 . The method of claim 30 , wherein the source of iron is selected from FeCl 3 , impure FeCl 3 and mixtures thereof, and the reducing agent is a Grignard reagent.

35 . The method of any one of claims 11 to 17 , wherein the reaction condition is a Suzuki-Miyaura coupling condition or a Sonogashira coupling condition, or other common Pd-catalyzed cross-coupling reactions.

36 . The method of claim 30 , wherein the reaction is performed at room temperature.

Assignees

• Univ California

Inventors

• Lipshutz Bruce H
• Handa Sachin

Classifications

• B01J35/45

  Nanoparticles · CPC title

• C07C205/12

  the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms · CPC title

• C07D317/46

  condensed with one six-membered ring · CPC title

• C07D471/04

  Ortho-condensed systems · CPC title

• B01J2531/842

  Iron · CPC title