Supporting InformationThe supporting information is available free of charge on the ACS Publications website at DOI: Synthetic methods, characterization, crystallographic and computational modeling data.
One air stable Cu(ii)-salen complex compound enables the generation of propargylamines. Mechanistic details, scope and limitations of this protocol are presented.
Pressure
on researchers to deliver new medicines to the patient
continues to grow. Attrition rates in the research and development
process present a significant challenge to the viability of the current
model of drug discovery. Analysis shows that increasing the three-dimensionality
of potential drug candidates decreases the risk of attrition, and
it is for this reason many workers have taken a new look at the power
of photochemistry, in particular photocycloadditions, as a means to
generate novel sp3-rich scaffolds for use in drug discovery
programs. The viability of carrying out photochemical reactions on
scale is also being addressed by the introduction of new technical
developments.
The hybrid bidentate 1‐(2‐pyridyl)benzotriazole (pyb) ligand was introduced into 3d transition metal catalysis. Specifically, [CuII(OTf)2(pyb)2]⋅2 CH3CN (1) enables the synthesis of a wide range of propargylamines by the A3 coupling reaction at room temperature in the absence of additives. Experimental and high‐level theoretical calculations suggest that the bridging N atom of the ligand imposes exclusive trans coordination at Cu and allows ligand rotation, while the N atom of the pyridine group modulates charge distribution and flux, and thus orchestrates structural and electronic precatalyst control permitting alkyne binding with simultaneous activation of the C−H bond via a transient CuI species.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.