Ylide-functionalised phosphanes for use in metal complexes and homogeneous catalysis

Patent metadata

Field	Value
Publication number	US-12521704-B2
Application number	US-202318545062-A
Country	US
Kind code	B2
Filing date	Dec 19, 2023
Priority date	Aug 8, 2017
Publication date	Jan 13, 2026
Grant date	Jan 13, 2026

Abstract

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions.

First claim

The invention claimed is:

1 . A process for performing a coupling reaction containing the steps of
providing a reaction mixture containing at least a substrate, a coupling partner, and a metal complex containing a phosphane ligands of formulas YPR 1 R 2 (I), Y 2 PR 1 (II) or Y 3 P (III)

where
Y represents an ylide substituent bound to the phosphorus atom through the carbanionic center and having onium groups On and X groups,
On, is phosphonium groups-P (R 3 R 4 R 5 ),
X, is cyano (—CN), and
R 1 , R 2 , R 3 , R 4 and R 5 , if any, are independently selected from alkyl, aryl and heteroaryl groups that may be unsubstituted or substituted with functional groups, and
reacting said substrate with said coupling partner in the presence of the metal complex to form a coupling product.

2 . The process according to claim 1 , wherein the metal of said metal complex is a transition metal.

3 . The process according to claim 1 , wherein the metal of said metal complex is a metal of group 10 or 11 of the Periodic Table of the elements.

4 . The process according to claim 1 , wherein the metal of said metal complex is selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, and combinations thereof.

5 . The process according to claim 1 , wherein the substrate is a substituted aromatic compound.

6 . The process according to claim 5 , wherein said substituted aromatic compound is an aromatic or heteroaromatic compound.

7 . The process according to claim 5 , wherein said substituted aromatic compound is substituted with a leaving group, or an unsaturated aliphatic group, or a leaving group.

8 . The process according to claim 7 , wherein said leaving group is selected from the group consisting of halogen, tosylate, nosylate and mesylate, or said unsaturated aliphatic group is selected from the group consisting of alkene or alkyne.

9 . The process according to claim 1 , wherein the coupling partner comprises an organometallic compound.

10 . The process according to claim 9 , wherein said organometallic compound is selected from the group consisting of organic boron compounds, organolithium compounds, organozinc compounds, organolithium compounds, and Grignard compounds.

11 . The process according to claim 9 , wherein said organometallic compound comprises of at least one aromatic residue.

12 . The process according to claim 9 , wherein said organometallic compound comprises of at least one unsaturated aliphatic residue.

13 . The process according to claim 9 , wherein said organometallic compound comprises of at least one saturated aliphatic residue.

14 . The process according to claim 1 , wherein said complex is a palladium allyl complex having the following structure (V) or (VI):

wherein X is an anion,
Y, R 1 , R 2 are defined as in claim 1 ,
R 33 , R 34 and R 35 are independently selected from H, alkyl, aryl and heteroaryl groups that may be unsubstituted or substituted with functional groups; or
at least two of R 33 , R 34 and R 35 form a carbocyclic ring with 5 to 14 carbon atoms,
Ar represents a substituted or unsubstituted, especially a substituted, aryl group.

15 . The process according to claim 14 , wherein R 33 , R 34 and R 35 are independently selected from linear, branched-chain or cyclic C 1-10 alkyl groups, the aryl groups are selected from C 6-14 aryl groups, the alkenyl groups are selected from mono-or polyunsaturated linear, branched-chain or cyclic C 2-10 alkenyl groups, and the heteroaryl groups are selected from C 6-14 heteroaryl groups;
and/or at least two of R 33 , R 34 and R 35 form a carbocyclic ring that is a C 4-10 cycloalkyl group, or a C 6-14 aryl group, which may be substituted with one or more functional groups; and Ar are selected from C 6-14 aryl groups, and the heteroaryl groups are selected from C 6-14 heteroaryl groups, wherein all of the groups mentioned above may be substituted with functional groups; and the functional groups are selected from alkyl (—R 11 ), especially C 1-6 alkyl groups, C 6-10 aryl (—R 12 ), halogen (—Hal), hydroxy (—OH), cyano (—CN), alkoxy (—OR 3 ), amino (—NR 112 , —NHR 11 , —NH 2 ), mercapto (—SH, —SR 11 ), wherein R 11 , independently of further R 11 residues, is selected from C 1-6 alkyl residues.

16 . The process according to claim 14 , wherein X is selected from the group of halogen, tosylate, nosylate and mesylate.

17 . The process according to claim 14 , wherein X is selected from the group of fluorine, chlorine, bromine, iodine, tosylate, nosylate and mesylate, and/or aryl is selected from phenyl, m-tolyl, p-tolyl, o-tolyl, mesityl, 1,3-diisopropylphenyl.

Assignees

• Umicore Ag & Co Kg

Inventors

• Däschlein-Gessner Viktoria
• Scherpf Thorsten

Classifications

• B01J2540/54

  Quaternary phosphonium groups · CPC title

• B01J2540/34

  Sulfonyl groups · CPC title

• B01J2531/824

  Palladium · CPC title

• B01J2531/18

  Gold · CPC title

• B01J2531/0205

  Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp · CPC title