Ti-catalyzed 1,2-Diamination of Alkynes Using 1,1-Disubstituted Hydrazines.

ABSTRACT: Ti-catalyzed alkyne diamination and alkyne hydrohydrazination proceed through a common N-aminoazatitanacyclobutene intermediate. These reactions have historically existed as processes catalyzed by distinct molecular Ti compounds, with several reports for hydrohydrazination and only a single example for diamination. Here, we demonstrate that a diamidoamine Ti catalyst, (NNN)Ti(═NNR₂) (1, (NNN)H₂ = N-methyl-N',N″-bis(trimethylsilyl)diethylenetriamine; R = alkyl, aryl), is capable of catalyzing both diamination and hydrohydrazination, where the selectivity is dictated by simple changes to the reaction conditions. This approach capitalizes on the fact that there are entropic differences at the selectivity branch point betwe

SUBMITTER: Karmakar PS 

PROVIDER: S-EPMC12035820 | biostudies-literature | 2025 Apr

REPOSITORIES: biostudies-literature