Mechanistic insights into nitric oxide generation from nitrite O-atom transfer in the unsymmetrical β-diketiminato copper(II) nitrite complex.

In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite PPh-induced oxygen atom transfer (OAT) in the unsymmetrical β-diketiminato copper(II), LCuONO. We discovered that the OAT process involves the cooperation of two PPh ligands and follows the mechanism distinct from that of the symmetrical β-diketiminato analogue. The Δ value, calculated to be 34.

Cyanopyridoimidazole/1,2-Aminothiol Click Reaction: A Novel Bioorthogonal Reaction for Synthesis of Radiotracers.

We herein described the design and synthesis of the cyanopyridoimidazoles (CPIs) as new bioorthogonal click reagents toward 1,2-aminothiol groups. Kinetic and density functional theory-based studies of the synthetic compounds revealed that incorporating an electron-withdrawing substituent into the CPI scaffold lowers its lowest unoccupied molecular orbital energy, consequently increasing reactivity. Optimized CPI showed rapid reactivity and high stability in physiological conditions and has been demonstrated to be suitable for various radiotracer synthetic methods.