69498-76-6Relevant academic research and scientific papers
Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru?N Bond
Shimbayashi, Takuya,Okamoto, Kazuhiro,Ohe, Kouichi
, p. 16892 - 16897 (2017/12/02)
The reaction of an oxime ester with [Ru(PPh3)3X2] proceeded smoothly at room temperature to afford a stable RuIV ketimido complex as oxidative adduct. The structure of the complex was unambiguously determined by X-ray crystallographic analysis, which showed an almost linear Ru?N?C array. The electronic properties of the nitrogen atom were estimated by DFT calculations, and the results suggested double-bond character of the Ru?N bond. Kinetic studies and consideration of the substituent effect on the oxime ester led to the proposal of a reaction mechanism involving oxidative addition, which could proceed by N,O-chelating coordination to the Ru center prior to N?O bond cleavage. The obtained Ru ketimido complex could be transformed into a ruthenacycle by C?H activation by a concerted metalation–deprotonation mechanism in dichloromethane/methanol. Ru ketimido complexes with a tethered alkyne or alkene moiety underwent chloroamination of unsaturated C?C bonds followed by C?H activation, which resulted in the formation of a ruthenacycle. Considering the LUMO of an isolated Ru ketimido complex, the chloroamination should proceed by a synchronous 1,3-dipolar cycloaddition-type mechanism. Insight into the character and reactivity of Ru ketimido complexes will be helpful for developments in the catalytic transformation of oxime esters.
N-substituted imines by the copper-catalyzed N-imination of boronic acids and organostannanes with O-acyl ketoximes
Liu, Songbai,Yu, Ying,Liebeskind, Lanny S.
, p. 1947 - 1950 (2008/02/02)
Catalytic quantities of copper(I) or copper(II) sources catalyze the N-imination of boronic acids and organostannanes through reaction with oxime O-carboxylates under nonbasic conditions. This method tolerates various functional groups and takes place efficiently using aryl, heteroaryl, and alkenyl boronic acids and stannanes.
