Ligands for metals and improved metal-catalyzed processes based thereon

A method, comprising the step of:

• combining a compound represented by ArX, a compound represented by HN(R′)R″, a catalyst complex comprising a transition metal and a ligand, and a base, thereby forming a compound represented by ArN(R′)R″:
• wherein
• Ar is selected from the group consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• X is selected from the group consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• R′ and R″ are selected, independently for each occurrence, from the group 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 two heteroatoms beyond the nitrogen to which R′ and R″ are bonded;
• R′ and/or R″ may be covalently linked to Ar;
• the transition metal is selected from the group consisting of the Group VIIIA metals;
• the ligand is selected from the group consisting of a compound represented by 2:
• wherein
• Q represent P(R)2;
• Y represents H, alkyl, N(R)2, OR, or SR;
• R, R1, R2, R3, R4, R5, R6, R7, and R8, independently for each occurrence represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imino, carboxamido, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, formyl, acyl, aldehyde, ester, heteroalkyl, nitrile, guanidine, amidine, acetal, ketal, amine oxide, aryl, heteroaryl, azide, aziridine, carbamate, epoxide, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or (CH2)mR80;
• R80 represents independently for each occurrence an unsubstituted or substituted aryl, a cycloalkyl, a cycloalkenyl, a heterocycle, or a polycycle;
• m is independently for each occurrence an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, may be provided in the form of a mixture of enantiomers or as a single enantiomer;
• and
• the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions.