Method for coupling a first compound to a second compound

Patent metadata

Field	Value
Publication number	US-10125082-B2
Application number	US-201515515069-A
Country	US
Kind code	B2
Filing date	Oct 8, 2015
Priority date	Oct 8, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

The present disclosure describes a method of coupling a first compound to a second compound, the method comprising: providing the first compound having a fluorosulfonate substituent; providing the second compound comprising an alkene; and reacting the first compound and the second compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound to the second compound.

First claim

What is claimed is:

1. A method of coupling a first compound A 1 to a second compound A 2 , the method comprising:
providing the first compound A 1 comprising an aryl group having a fluorosulfonate substituent of the formula —OSO 2 F or heteroaryl group having a fluorosulfonate substituent of the formula —OSO 2 F;
providing the second compound A 2 :

wherein each R substituent is independently Hydrogen, an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a nitro group, a halide, a nitrogen, a cyano group, a carboxyester group, an acetoxy group, a substituted alkyl, aryl, heteroaryl or cycloalkyl group, or any two of the R groups are constituent parts of a ring system; and
reacting the first compound A 1 and the second compound A 2 in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound A 1 to the second compound A 2 .

2. The method of claim 1 , wherein the reaction mixture further includes a ligand.

3. The method of claim 1 wherein the catalyst is generated in-situ from a palladium precatalyst.

4. The method of claim 1 wherein the catalyst is generated in-situ from a palladium precatalyst, the palladium precatalyst is selected from the group consisting of: Palladium(II) acetate, Palladium(II) chloride, Dichlorobis(acetonitrile)palladium(II), Dichlorobis(benzonitrile)palladium(II), Allylpalladium chloride dimer, Palladium(II) acetyl acetonate, Palladium(II) bromideBis(dibenzylideneacetone)palladium(0), Bis(2-methylallyl)palladium chloride dimer, Crotylpalladium chloride dimer, Dichloro(1,5-cyclooctadiene)palladium(II), Dichloro(norbornadiene)palladium(II), Palladium(II) trifluoroacetate, Palladium(II) benzoate, Palladium(II) trimethylacetate, Palladium(II) oxide, Palladium(II) cyanide, Tris(dibenzylideneacetone)dipalladium(0), Palladium(II) hexafluoroacetylacetonate, cis-Dichloro(N,N,N′,N′-tetramethylethylenediamine)palladium(II), and Cyclopentadienyl[(1,2,3-n)-1-phenyl-2-propenyl]palladium(II), [1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride, and (1,3-Bis(2,6-diisopropylphenyl)imidazolidene) (3-chloropyridyl) palladium(II) dichloride, and a mixture of two or more thereof.

5. The method of claim 2 wherein the ligand is a phosphine ligand or a carbene ligand.

6. The method of claim 2 wherein the ligand is an amine-based ligand, an aminophosphine-based ligand, an N-heterocyclic carbene-based ligand, a monodentate or bidentate alkyl amine, or a monodentate or bidentate aromatic amine.

7. The method of claim 1 wherein the reaction mixture includes a base.

8. The method of claim 7 , wherein the base is a carbonate salt, a phosphate salt, an acetate salt or a carboxylic acid salt.

9. The method of claim 7 , wherein the base is selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, ammonium carbonate, substituted ammonium carbonates, hydrogen carbonates, lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, cesium phosphate, ammonium phosphate, substituted ammonium phosphates, hydrogen phosphates, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, ammonium acetate, substituted ammonium acetates, formate salts, fluoroacetate salts, propionate anions with lithium, sodium, potassium, rubidium, cesium, ammonium, and substituted ammonium cations, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium dihydroxide, calcium dihydroxide, strontium dihydroxide, and barium dihydroxide, aluminum trihydroxide, gallium trihydroxide, indium trihydroxide, thallium trihydroxide, triethylamine, N,N-diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-Diazabicyclo[4.3.0]non-5-ene, 1,8-Diazabicyclo[5.4.0]undec-7-ene, lithium, sodium, and potassium salts of bis(trimethylsilyl)amide, lithium, sodium, and potassium salts oft butoxide, 1,8-bi s(dimethylamino)naphthalene, pyridine, morpholine, 2,6-lutidine, triethylamine., N,N-Dicyclohexylmethylamine, diisopropylamine, sodium fluoride, potassium fluoride, cesium fluoride, silver fluoride, tetra butyl ammonium fluoride, ammonium fluoride, triethyl ammonium fluoride and a mixture of two or more thereof.

10. The method of claim 1 , wherein the reaction mixture includes a solvent.

11. The method of claim 10 , wherein the solvent is selected from the group consisting of toluene, xylene, benzene, chlorobenzene, water, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, pentanol, hexanol, tent-butyl alcohol, tent-amyl alcohol, ethylene glycol, 1,2- propanediol, 1,3-propanediol, glycerol, N-methyl-2-pyrrolidone, acetonitrile, N,N-dimethylformamide, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, triacetin, acetone, methyl ethyl ketone, ethereal solvents, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, diethylether, cyclopenyl methyl ether, 2-butyl ethyl ether, dimethoxyethane, polyethyleneglycol, dimethylacetamide(DMA), dimethylsulfoxide (DMSO), and 1,2-dichloroethane (DCE).

12. The method of claim 1 , wherein the reaction mixture includes water.

13. A method for coupling a first compound A 1 to a second compound A 2 , as illustrated in Equation 1, comprising :

providing sulfuryl fluoride, a base and the first compound A 1 comprising an aryl having a hydroxyl substituent or a heteroaryl group having a hydroxyl substituent to a reaction mixture, the first compound comprising an aryl or a heteroaryl group;
providing a catalyst having at least one group 10 atom and the second compound A 2 to the reaction mixture:

wherein each R substituent is independently Hydrogen, an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a nitro group, a halide, a nitrogen, a cyano group, a carboxyester group, an acetoxy group, a substituted alkyl, aryl, heteroaryl or cycloalkyl group, or any two of the R groups are constituent parts of a ring system; and
allowing the reaction mixture to react under conditions to produce the product shown in Equation 1.

14. The method of claim 13 , wherein the reaction mixture further includes a ligand, and a base.

15. The method of claim 13 wherein the catalyst is generated in-situ from a palladium precatalyst.

16. The method of claim 14 wherein the ligand is a phosphine ligand or a carbene ligand.

17. The method of claim 14 wherein the ligand is an amine-based ligand, an aminophosphine-based ligand or an N-heterocyclic carbene-based ligand.

18. The method of claim 14 wherein the ligand is a monodentate or bidentate alkyl amine or a monodentate or bidentate aromatic amine.

19. The method of claim 14 , wherein the base is a carbonate salt, a phosphate salt, an acetate salt or a carboxylic acid salt.

20. The method of claim 13 , wherein the reaction mixture includes a solvent.

Assignees

• Dow Global Technologies Llc

Inventors

• Hanley Patrick S
• Oppenheimer Jossian
• Ober Matthias S
• Kruper Jr William J
• Krasovskiy Arkady L

Classifications

• C07C2531/20

  Carbonyls · CPC title

• C07C69/65

  of unsaturated acids · CPC title

• C07C233/65

  having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals · CPC title

• C07D317/60

  Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07C67/31

  by introduction of functional groups containing oxygen only in singly bound form · CPC title