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CN-114555615-B - Complex compound

CN114555615BCN 114555615 BCN114555615 BCN 114555615BCN-114555615-B

Abstract

A compound of formula (I) wherein M is Pd (II) or Ni (II), X is a halide, R 1 and R 2 are independently an organic group having 1 to 20 carbon atoms, or R 1 and R 2 are bonded to a phosphorus atom to form a ring structure, R 3 is an organic group having 1 to 20 carbon atoms, provided that R 1 、R 2 、R 3 are not all phenyl groups.

Inventors

  • R. Kahan
  • M. Pitak
  • C. Xi chulin

Assignees

  • 庄信万丰股份有限公司

Dates

Publication Date
20260512
Application Date
20200803
Priority Date
20191219

Claims (10)

  1. 1. A compound of formula (I) Wherein M is Pd (II); X is a halide; R 1 and R 2 are independently an organic group having 1 to 20 carbon atoms selected from the group consisting of alkyl, cycloalkyl and aryl; R 3 is an organic group having 1 to 20 carbon atoms selected from alkyl, cycloalkyl, aryl and metallocene groups; Provided that R 1 、R 2 、R 3 is not all phenyl.
  2. 2. The compound of claim 1, wherein X is Cl, br or I.
  3. 3. The compound of claim 2, wherein X is Cl or Br.
  4. 4. A compound of formula (I) Wherein M is Pd (II); X is a halide; PR 1 R 2 R 3 is selected from: Ad=adamantyl Cy=cyclohexyl Bn=benzyl group Ar=2, 6 dimethoxyphenyl group Mes=2, 4, 6-trimethylphenyl.
  5. 5. A process for preparing a compound of formula (IA) [M 2 Cl 6 ][HPR 1 R 2 R 3 ] 2 (IA) Wherein M is Pd (II); R 1 and R 2 are independently an organic group having 1 to 20 carbon atoms selected from the group consisting of alkyl, cycloalkyl and aryl; And R 3 is an organic group having 1 to 20 carbon atoms selected from alkyl, cycloalkyl, aryl and metallocene groups Provided that R 1 、R 2 and R 3 are not both phenyl, The method comprises the step of reacting a compound of formula H 2 PdCl 4 with the ligand PR 1 R 2 R 3 or a salt thereof.
  6. 6. A process for preparing a compound of formula (IB) [M 2 X' 6 ][HPR 1 R 2 R 3 ] 2 (IB) Wherein M is Pd (II); R 1 and R 2 are independently an organic group having 1 to 20 carbon atoms selected from the group consisting of alkyl, cycloalkyl and aryl; R 3 is an organic group having 1 to 20 carbon atoms selected from alkyl, cycloalkyl, aryl and metallocene groups; And X 'is bromide, iodide or fluoride, comprising the step of reacting a compound of formula H 2 PdCl 4 with the ligand PR 1 R 2 R 3 or a salt thereof and a compound ZX', wherein Z is hydrogen or a monovalent metal ion.
  7. 7. A process for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, the process comprising using a compound according to any one of claims 1 to 4.
  8. 8. Use of a compound according to any one of claims 1 to 4 for catalyzing a carbon-carbon coupling reaction.
  9. 9. A process for carrying out a carbon-heteroatom coupling reaction in the presence of a catalyst, the process comprising using a compound according to any one of claims 1 to 4.
  10. 10. Use of a compound according to any one of claims 1 to 4 for catalyzing a carbon-heteroatom coupling reaction.

Description

Complex compound Technical Field The present invention relates to transition metal complexes and in particular to metal (II) dimer complexes. The invention further relates to a process for preparing these complexes and to the use of these complexes for catalyzing cross-coupling reactions. Background Palladium (II) complexes comprising phosphine ligands are known as active catalysts for cross-coupling reactions. For example, catalysts PdCl 2(AmPhos)2, amPhosPd (crotyl) Cl, XPhosPd (crotyl) Cl, ruPhosPd (crotyl) Cl, and [ BrettPhosPd (crotyl) ] OTf are commercially available from Johnson MATTHEY PLC. Palladium (II) dimers are also known to be useful in certain cross-coupling reactions. For example Naghipour et al (polyhedron (Polyhedron), 105, 2016, pages 18-26) indicate [Pd2Br6][Ph3PCH2C6H4CH2OC(O)CH3]2 is useful in Stille cross-coupling reactions. Evans et al (society of chemistry (J.chem. Soc.), "Dalton journal (Dalton Trans.)), 2002, pages 2207-2212 disclose [ Pd 2I6][NEt3H]2 ] formed in situ and which is used as a pre-catalyst. The present inventors have developed alternative palladium (II) complexes with a simple preparation route using more environmentally friendly solvents. Disclosure of Invention The present invention provides a compound of formula (I) Wherein: m is Pd (II) or Ni (II); X is a halide; R 1 and R 2 are independently an organic group having 1 to 20 carbon atoms, or R 1 and R 2 are linked to a phosphorus atom to form a ring structure; r 3 is an organic group having 1 to 20 carbon atoms; Provided that R 1、R2、R3 is not all phenyl. The present invention also provides a process for preparing a compound of formula (IA) [M2Cl6][HPR1R2R-3]2 (IA) Wherein M, R 1、R2 and R 3 are as defined above, comprising the step of reacting a compound of formula H 2PdCl4 with the ligand PR 1R2R3 or salt thereof. The present invention also provides a process for preparing a compound of formula (IB) [M2X'6][HPR1R2R-3]2 (IB) Wherein M, R 1、R2 and R 3 are as defined above and X 'is bromide, iodide or fluoride, the method comprising the step of reacting a compound of formula H 2PdCl4 with a ligand PR 1R2R3 or salt thereof and a compound ZX', wherein Z is hydrogen or a metal. The present invention also provides a process for carrying out a carbon-carbon coupling reaction in the presence of a catalyst, which comprises using a compound of formula (I) as defined above. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing a carbon-carbon coupling reaction. The present invention also provides a process for carrying out a carbon-heteroatom coupling reaction which comprises the use of a compound of formula (I) as defined hereinabove. Alternatively, the present invention provides the use of a compound of formula (I) as defined above for catalyzing a carbon-heteroatom linkage reaction. Drawings FIG. 1 shows the crystal structure of [ HSPhos ] 2[Pd2Br6 ]. FIG. 2 shows the crystal structure of [ HtBuXPhos ] 2[Pd2Cl6 ]. FIG. 3 shows the crystal structure of [ HPCy 3]2[Pd2Cl6 ]. FIG. 4 shows the crystal structure of [ HP (2, 4, 6-trimethylphenyl) 3]2[Pd2Cl6 ]. Definition of the definition The attachment point of a moiety or substituent is indicated by "-". For example, -OH is attached through an oxygen atom. "Alkyl" refers to a straight or branched saturated hydrocarbon group. In certain embodiments, the alkyl group has 1 to 20 carbon atoms. In other embodiments, the alkyl group has 1 to 15 carbon atoms. In other embodiments, the alkyl group has 1 to 8 carbon atoms. Unless otherwise indicated, alkyl groups are attached at any suitable carbon atom. The alkyl group may be unsubstituted. Alternatively, the alkyl group may be substituted at any suitable carbon atom. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and the like. "Alkoxy" refers to an optionally substituted group of the formula alkyl-O-or cycloalkyl-O-, wherein alkyl and cycloalkyl are as defined herein. "Alkoxyalkyl" refers to an optionally substituted group of the formula alkoxy-alkyl-, wherein alkoxy and alkyl are as defined herein. "Cycloalkyl" refers to a saturated carbocyclic hydrocarbon group. Cycloalkyl groups may have a single ring or multiple condensed rings. In certain embodiments, cycloalkyl groups have 3 to 15 carbon atoms. In other embodiments, the cycloalkyl group has 3 to 10 carbon atoms. In other embodiments, the cycloalkyl group has 6 to 10 carbon atoms. Unless otherwise indicated, cycloalkyl groups are attached at any suitable carbon atom. Cycloalkyl groups may be unsubstituted. Alternatively, the cycloalkyl group may be substituted at any suitable carbon atom. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like. "Aryl" refers to an aromatic carbocyclic group. The aryl group may have a single ring or mu