Synthesis of Titanium Complexes Supported by Carbinolamide- and Amide-Containing Ligands Derived from Ti(NMe2)4-Mediated Selective Amidations of Carbonyl Groups.

An efficient strategy for the syntheses of a series of titanium complexes has been developed. This protocol features the employment of Ti(NMe2)4 both as the metal center to trigger the deprotonation of the ligands and as an amine source to proceed the amidation reactions of carbonyl functionalities of the ligands. Treatment of Ti(NMe2)4 with a ligand HL1 (HL1 = 2,2'-(((2-hydroxybenzyl)azanediyl)bis(ethane-2,1-diyl))bis(isoindoline-1,3-dione) results in the formation of Ti(L1')(NMe2) (1) (H3L1' = N1-(2-((2-(1-(dimethylamino)-1-hydroxy-3-oxoisoindolin-2-yl)ethyl)(2-hydroxybenzyl)amino)ethyl)-N2,N2-dimethylphthalamide). One important feature regarding the synthesis of 1 is the occurrence of the in situ metal-ligand reaction between Ti(NMe2)4 and HL1, leading to the simultaneous formations of carbinolamide and amide scaffolds. Another prominent feature in terms of the preparation of 1 is the achievement of the selective ring-opening reaction of one of the two phthalimide units of the HL1 ligand, affording carbinolamide and amide functionalities within one ligand set. The developed methodology characterizes an ample substrate scope. The selective amidation reactions of the carbonyl groups have been realized for a series of analogous ligands HL2-HL7. Density functional theory calculations were employed to disclose the mechanisms for the formation of 1-7, and the details for the selective ring-opening reactions of the phthalimide unit were uncovered.