3387-25-5Relevant articles and documents
Extremely Long Lived Localized Singlet Diradicals in a Macrocyclic Structure: A Case Study on the Stretch Effect
Harada, Yuta,Wang, Zhe,Kumashiro, Shunsuke,Hatano, Sayaka,Abe, Manabu
, p. 14808 - 14815 (2018)
Localized singlet diradicals have attracted much attention, not only in the field of bond-homolysis chemistry, but also in nonlinear optical materials. In this study, an extremely long lived localized singlet diradical was obtained by using a new molecular design strategy in which it is kinetically stabilized by means of a macrocycle that increases the molecular strain of the corresponding σ-bonded compound. Notably, the lifetime of this diradical (14 μs) is two orders of magnitude longer than that of a standard singlet diradical without a macrocyclic structure (≈0.2 μs) at 293 K. The species is persistent below a temperature of 100 K. In addition to the kinetic stabilization of the singlet diradical, the spontaneous oxidation of its corresponding ring-closed compound at 298 K produced oxygenated products under atmospheric conditions. Apparently, the “stretch effect” induced by the macrocyclic structure plays a crucial role in extending the lifetime of localized singlet diradicals and increasing the reactivity of their corresponding σ-bonded compounds.
PhIO/Et3N ? 3HF-Mediated Formation of Fluorinated 2H-Azirines via Domino Fluorination/Azirination Reaction of Enamines
Zhang, Yong,Zhao, Xiaoyuan,Zhuang, Chen,Wang, Senlin,Zhang-Negrerie, Daisy,Du, Yunfei
supporting information, p. 2107 - 2112 (2018/04/19)
A variety of enamine carboxylic esters and enaminones were converted to the biologically interesting fluorinated 2H-azirines through reactions with PhIF2 generated in situ by PhIO and Et3N ? 3HF in 1,2-dichroloethane, which features the hypervalent iodine reagents-mediated introduction of fluorine atom and formation of the 2H-azirine skeleton under metal-free conditions. The domino reaction is postulated to proceed via a PhIF2-mediated oxidative fluorination and a subsequent azirination of the fluorinated enamine intermediates. (Figure presented.).
