Ligands for metals and improved metal-catalyzed processes based thereon

The method depicted in Scheme 1:

• wherein
• Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• X is selected from the set consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• R′ and R″ are selected, independently for each occurrence, from the set consisting of H, alkyl, heteroalkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl;
• R′ and R″, taken together, may form an optionally substituted ring consisting of 3-10 backbone atoms inclusive;
• said ring optionally comprising one or more heteroatoms beyond the nitrogen to which R′ and R″ are bonded;
• R′ and/or R″ may be covalently linked to Ar such that the amination reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 2:

• wherein
• Ar and Ar′ are independently selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• X is selected from the set consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and Ar′ may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 3:

• wherein
• Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• R is selected from the set consisting of optionally substituted alkyl, heteroalkyl, and aralkyl;
• R′ is selected, independently for each occurrence, from the set of alkyl and heteroalkyl;
• the carbon-boron bond of said alkyl and heteroalkyl groups being inert under the reaction conditions, e.g., BR′2 taken together represents 9-borobicyclo[3.3.1]nonyl.
• X is selected from the set consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and R may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 4:

• wherein
• Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• R, R′, and R″ are selected, independently for each occurrence, from the set consisting of H, alkyl, heteroalkyl, aralkyl, aryl, heteroaryl;
• X is selected from the set consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and one of R, R′, and R″ may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.