Use of a catalyst composition for biaryl synthesis by decarboxylative cross-coupling

Patent metadata

Field	Value
Publication number	US-2023406826-A1
Application number	US-202318306624-A
Country	US
Kind code	A1
Filing date	Apr 25, 2023
Priority date	Jun 21, 2022
Publication date	Dec 21, 2023
Grant date	—

Abstract

The present invention relates to a process for coupling a heterocyclic aromatic ring AR1 and a carbocyclic or heterocyclic aromatic ring AR2 to each other by a light-assisted decarboxylative carbon-carbon cross-coupling reaction, wherein
a reaction medium is provided by mixing a first reactant, a second reactant and a catalyst composition, wherein the catalyst composition comprises (i) a palladium compound which is a palladium salt or a palladium complex or a mixture thereof, and (ii) a polycyclic compound of Formula (I), (II) or (III):

the reaction medium is irradiated by an external light source, thereby coupling the heterocyclic aromatic ring AR1 of the first reactant to the aromatic ring AR2 of the second reactant by a decarboxylative carbon-carbon cross-coupling reaction.

First claim

1 . A process which comprises
mixing a first reactant, a second reactant and a catalyst composition, thereby providing a reaction medium, wherein
the first reactant is a compound which comprises a heterocyclic aromatic ring AR1 to which a carboxylic acid group, a carboxylate group or a carboxylic acid ester group is attached,
the second reactant is a compound which comprises an aromatic ring AR2 to which a halogen atom, a pseudohalogen group or a sulfonate group is attached,
the catalyst composition comprises

(i) a palladium compound which is selected from a palladium salt or a palladium complex or a mixture thereof,
(ii) a polycyclic compound of Formula (I), (II) or (III):

wherein in Formula (I)
n is 0 or 1;
X is O, C(R 10 )(R 11 ), or N(R 12 );
R 1 to R 12 are selected independently from each other from hydrogen, aryl and C 1-10 alkyl, wherein aryl and C 1-10 alkyl are optionally substituted with one or more substituents R 13 ;
wherein the one or more substituents R 13 , if present, are selected independently from each other from C 1-6 alkyl, C 1-6 haloalkyl, —OH, —O—(C 1-6 alkyl), —NO 2 , —CN, halogen, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —C(═O)OH, —C(═O)O—(C 1-6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1-6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1-6 alkyl), —S(O) 2 N(C 1-6 alkyl)(C 1-6 alkyl), —S—(C 1-6 alkyl), —S(O)(C 1-6 alkyl), —S(O) 2 (C 1-6 alkyl), —S-(phenyl), —S(O)(phenyl), —S(O) 2 (phenyl), and a N-carbazolyl of Formula (1.1)

wherein in Formula (II)
R 1 is selected from C 1-16 alkyl and aryl, each of which is optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms;

R 2 to R 11 are selected independently from each other from hydrogen, C 1-16 alkyl, aryl and heteroaryl, wherein C 1-16 alkyl, aryl and heteroaryl are optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms; or at least two of the residues R 2 to R 11 which are adjacent to each other form together with the carbon atoms to which they are attached a five- or six-membered aromatic ring and, if present, the remaining residues are selected independently from each other from hydrogen, C 1-16 alkyl, aryl and heteroaryl, wherein C 1-16 alkyl, aryl and heteroaryl are optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms;
wherein the one or more substituents R 12 , if present, are selected independently from each other from C 1-6 alkyl, C 1-6 haloalkyl, —OH, —O—(C 1-6 alkyl), —NO 2 , —CN, halogen, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —C(═O)OH, —C(═O)O—(C 1-6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1-6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1-6 alkyl), —S(O) 2 N(C 1-6 alkyl)(C 1-6 alkyl), —S—(C 1-6 alkyl), —S(O)(C 1-6 alkyl), —S(O) 2 (C 1-6 alkyl), —S-(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl),

wherein in Formula (III)
R 1 is selected from C 1-16 alkyl and aryl, each of which is optionally substituted with one or more substituents R 11 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms;
R 2 to R 9 are selected independently from each other from hydrogen, C 1-16 alkyl and aryl, wherein C 1-16 alkyl and aryl are optionally substituted with one or more substituents R 11 , and/or C 1-6 alkyl is optionally interrupted by one or more oxygen atoms;
R 10 is aryl which is optionally substituted with one or more substituents R 2 ;
wherein the one or more substituents R 11 , if present, are selected independently from each other from C 1-6 alkyl, C 1-6 haloalkyl, —OH, —O—(C 1-6 alkyl), —NO 2 , —CN, halogen, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —C(═O)OH, —C(═O)O—(C 1-6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1-6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1-6 alkyl), —S(O) 2 N(C 1-4 alkyl)(C 1-6 alkyl), —S—(C 1-6 alkyl), —S(O)(C 1-6 alkyl), —S(O) 2 (C 1-6 alkyl), —S-(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
wherein the one or more substituents R 12 , if present, are selected independently from each other from C 1-6 alkyl and aryl, wherein aryl is optionally substituted with one or more C 1-6 alkyl;

irradiating the reaction medium by an external light source, thereby coupling the heterocyclic aromatic ring AR1 of the first reactant to the aromatic ring AR2 of the second reactant by a decarboxylative carbon-carbon cross-coupling reaction.

2 . A process which comprises
mixing a reactant and a catalyst composition, thereby providing a reaction medium, wherein
the reactant is a compound which comprises a heterocyclic aromatic ring AR1 to which a carboxylic acid group, a carboxylate group or a carboxylic acid ester group is attached and an aromatic ring AR2 to which a halogen atom, a pseudohalogen group or a sulfonate group is attached,
the catalyst composition comprises
(i) a palladium compound which is selected from a palladium salt or a palladium complex or a mixture thereof,
(ii) a polycyclic compound of Formula (I), (II) or (III):

wherein in Formula (I)
n is 0 or 1;
X is O, C(R 10 )(R 11 ), or N(R 12 );
R 1 to R 12 are selected independently from each other from hydrogen, aryl and C 1-10 alkyl, wherein aryl and C 1-10 alkyl are optionally substituted with one or more substituents R 13 ;
wherein the one or more substituents R 13 , if present, are selected independently from each other from C 1-6 alkyl, C 1-6 haloalkyl, —OH, —O—(C 1-6 alkyl), —NO 2 , —CN, halogen, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —C(═O)OH, —C(═O)O—(C 1-6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1-6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1-6 alkyl), —S(O) 2 N(C 1-6 alkyl)(C 1-6 alkyl), —S—(C 1-6 alkyl), —S(O)(C 1-6 alkyl), —S(O) 2 (C 1-6 alkyl), —S-(phenyl), —S(O)(phenyl), —S(O) 2 (phenyl), and a N-carbazolyl of Formula (1.1)

wherein in Formula (II)
R 1 is selected from C 1-16 alkyl and aryl, each of which is optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms;
R 2 to R 11 are selected independently from each other from hydrogen, C 1-16 alkyl, aryl and heteroaryl, wherein C 1-16 alkyl, aryl and heteroaryl are optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms; or at least two of the residues R 2 to R 11 which are adjacent to each other form together with the carbon atoms to which they are attached a five- or six-membered aromatic ring and, if present, the remaining residues are selected independently from each other from hydrogen, C 1-16 alkyl, aryl and heteroaryl, wherein C 1-16 alkyl, aryl and heteroaryl are optionally substituted with one or more substituents R 12 , and/or C 1-16 alkyl is optionally interrupted by one or more oxygen atoms;
wherein the one or more substituents R 12 , if present, are selected independently from each other from C 1-6 alkyl, C 1-6 haloalkyl, —OH, —O—(C 1-6 alkyl), —NO 2 , —CN, halogen, —NH 2 , —NH(C 1-6 alkyl), —N(C 1-6 alkyl) 2 , —C(═O)OH, —C(═O)O—(C 1-6 alkyl), —C(═O)O-ph

Assignees

• Heraeus Deutschland Gmbh & Co Kg
• New Iridium Inc

Inventors

• Lim Chern-Hooi
• Qian Gang
• Elder William Zachary
• Riley Paige
• Kolvenbach Robin
• Walter Philipp
• Gock Michael

Classifications

• C07D213/26 Primary

  Radicals substituted by halogen atoms or nitro radicals · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J31/2234

  Beta-dicarbonyl ligands, e.g. acetylacetonates · CPC title

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title

• C07D209/58

  [b]- or [c]-condensed · CPC title