Methods for producing borylated arenes

• US 10,112,960 B2
• Filed: 09/05/2014
• Issued: 10/30/2018
• Est. Priority Date: 09/05/2013
• Status: Active Grant

• Current Assignee: Dow Agrosciences LLC (Corteva, Inc.), The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.), Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Smith, Milton R., Maleczka, Robert E., Li, Hao, Jayasundara, Chathurika R. K., Oppenheimer, Jossian, Sabasovs, Dmitrijs
• Primary Examiner(s): Kosack, Joseph R
• Application Number:
  US14/478,581
• Publication Number:
  US 20150065743A1
• Time in Patent Office: 1,516 Days
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/57 containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
• CPC Class Codes: C07C 67/343 by increase in the number of carbon atoms
• CPC Class Codes: C07C 69/76 Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C07F 15/04 Nickel compounds
• CPC Class Codes: C07F 5/025 Boronic and borinic acid compounds

Abstract

Methods for the selective borylation of arenes, including arenes substituted with an electron-withdrawing group (e.g., 1-chloro-3-fluoro-2-substituted benzenes) are provided. The methods can be used, in some embodiments, to efficiently and regioselectively prepare borylated arenes without the need for expensive cryogenic reaction conditions.

Claims

1. A method of forming a borylated arene comprising:

providing a substrate comprising a substituted arene ring comprising from 1 to 4 substituents, wherein the arene ring is unsubstituted at a first position that is electronically favored for CH-activation and unsubstituted at a second position that is sterically favored for CH-activation; and

contacting the substrate with an iridium precursor complex, an electron deficient bidentate ligand comprising at least one nitrogen heteroatom, and a borylation reagent under conditions effective to form a first borylated arene and optionally a second borylated arene;

wherein the electron deficient bidentate ligand comprises a compound defined by Formula IVa

2. The method of claim 1, wherein the arene ring comprising from 1 to 3 substituents.

3. The method of claim 1, wherein the arene ring is substituted with an electron withdrawing group selected from the group consisting of —

F and —

CF₃.

4. The method of claim 1, wherein the substrate comprises a phenyl ring substituted with an electron withdrawing group selected from the group consisting of —

F and —

CF₃, unsubstituted in a position ortho to the electron withdrawing group, and unsubstituted in a position meta to the electron withdrawing group,

wherein the first borylated arene comprises a phenyl ring substituted with an electron withdrawing group selected from the group consisting of —

F and —

CF₃, and a boronic acid or a boronic acid derivative in a position ortho to the electron withdrawing group, and

wherein the second borylated arene, when formed, comprises a phenyl ring substituted with an electron withdrawing group selected from the group consisting of —

F and —

CF₃, and a boronic acid or a boronic acid derivative in a position meta to the electron withdrawing group.

5. The method of claim 1, wherein the substrate comprises a pyridine ring selected from the group consisting of a 2-, 4-disubstituted pyridine ring, a 2-, 6-disubstituted pyridine ring, a 2-, 4-, 6-trisubstituted pyridine ring, and a 2-substituted pyridine ring.

6. The method of claim 1, wherein the substrate comprises a compound defined by Formula I

7. The method of claim 1, wherein the substrate comprises a 1-chloro-3-fluoro-2-substituted benzene.

8. The method of claim 7, wherein the substrate comprises 1-chloro-3-fluoro-2-methoxybenzene, and wherein the first borylated arene comprises (4-chloro-2-fluoro-3-methoxyphenyl)boronic acid or a (4-chloro-2-fluoro-3-methoxyphenyl)-boronic acid derivative.

9. The method of claim 1, wherein the iridium precursor complex comprises an iridium complex selected from the group consisting of an Ir(I)-cyclooctadiene precursor complex, an Ir(I)-cyclooctene precursor complex, an Ir(I)-mesitylene precursor complex, an Ir(I)-phosphine precursor complex, an Ir(I)-1,2,3,4,5-methylcyclopentadienyl precursor complex, and combinations thereof.

10. The method of claim 1, wherein the substrate, first borylated arene, and second borylated arene, when formed, comprise a substituent selected from the group consisting of —

Cl and —

Br.

11. The method of claim 10, wherein the substrate comprises a compound defined by the formula below

12. The method of claim 11, wherein the method further comprises reductively dehalogenating the first borylated arene to obtain a dehalogenated borylated arene.

13. The method of claim 1, further comprising contacting the first borylated arene or the dehalogenated borylated arene with a reactant selected from the group consisting of an aryl halide, an aryl pseudohalide, a vinyl halide, and a vinyl pseudohalide, and a transition metal catalyst to cross-couple the first borylated arene or the dehalogenated borylated arene and the reactant.