Synthesis of aminoarylboronic esters and substituted anilines from arenes via catalytic C-H activation/borylation/amination and uses thereof

A process for C—N coupling an aryl halide to an aminoarylboronic ester via the amine functionality of the aminoarylboronic ester which comprises:

• (a) reacting in a reaction vessel an aryl compound with a borane selected from the group consisting of a borane with a B—H, B—B, and B—Si bond in the presence of a catalytically effective amount of an iridium or rhodium complex with three or more substituents, and an organic ligand selected from the group consisting of phosphorus, carbon, nitrogen, oxygen, and sulfur organic ligands under anhydrous conditions to produce an arylboronic ester;
• (b) aminating the arylboronic ester formed in the reaction vessel with an organic compound containing an amine moiety in the presence of a catalytically effective amount of a metal catalyst complex under anhydrous conditions wherein the organic compound is coupled to the aryl group of the arylboronic ester compound to produce the aminoarylboronic ester;
• and
• (c) reacting the aminoarylboronic ester with the aryl halide in the presence of a palladium metal catalyst complex under anhydrous conditions to couple the aryl halide to the amine functionality of the aminoarylboronic ester.

A process for C—C coupling an aryl halide to an aminoarylboronic ester via the borane functionality of the aminoarylboronic ester which comprises:

• (a) reacting in a reaction vessel an aryl compound with a borane selected from the group consisting of a borane with a B—H, B—B, and B—Si bond in the presence of a catalytically effective amount of an iridium or rhodium complex with three or more substituents, and an organic ligand selected from the group consisting of phosphorus, carbon, nitrogen, oxygen, and sulfur organic ligands under anhydrous conditions to produce an arylboronic ester;
• (b) aminating the arylboronic ester formed in the reaction vessel with an organic compound containing an amine moiety in the presence of a catalytically effective amount of a metal catalyst complex under anhydrous conditions wherein the organic compound is coupled to the aryl group of the arylboronic ester compound to produce the aminoarylboronic ester;
• and
• (c) reacting the aminoarylboronic ester with the aryl halide in the presence of a palladium metal catalyst complex in the presence of water to couple the aryl halide to the aminoarylboronic ester.

A process for producing a substituted phenol amine which comprises:

• (a) reacting in a reaction vessel an aryl compound with a borane selected from the group consisting of a borane with a B—H, B—B, and B—Si bond in the presence of a catalytically effective amount of an iridium or rhodium complex with three or more substituents, and an organic ligand selected from the group consisting of phosphorus, carbon, nitrogen, oxygen, and sulfur organic ligands under anhydrous conditions to produce an arylboronic ester;
• (b) aminating the arylboronic ester formed in the reaction vessel with an organic compound containing an amine moiety in the presence of a catalytically effective amount of a metal catalyst complex under anhydrous conditions wherein the organic compound is coupled to the aryl group of the arylboronic ester compound to produce an aminoarylboronic ester;
• and
• (c) oxidizing the aminoarylboronic ester with a hydrogenating oxidizing compound to produce the substituted phenol amine.