37055-53-1Relevant articles and documents
Photo-induced Metal-Catalyst-Free Aromatic Finkelstein Reaction
Li, Lu,Liu, Wenbo,Zeng, Huiying,Mu, Xiaoyue,Cosa, Gonzalo,Mi, Zetian,Li, Chao-Jun
supporting information, p. 8328 - 8331 (2015/07/15)
The facile iodination of aromatic compounds under mild conditions is a great challenge for both organic and medicinal chemistry. Particularly, the synthesis of functionalized aryl iodides by light has long been considered impossible due to their photo-lability, which actually makes aryl iodides popular starting materials in many photo-substitution reactions. Herein, a photo-induced halogen exchange in aryl or vinyl halides has been discovered for the first time. A broad scope of aryl iodides can be prepared in high yields at room temperature under exceptionally mild conditions without any metal or photo-redox catalysts. The presence of a catalytic amount of elemental iodine could promote the reaction significantly.
Photoswitchable catalysts: Correlating structure and conformational dynamics with reactivity by a combined Experimental and computational approach
Stoll, Ragnar S.,Peters, Maike V.,Kuhn, Andreas,Hecht, Stefan,Heiles, Sven,Thiele, Christina M.,Goddard, Richard,Buehl, Michael
supporting information; experimental part, p. 357 - 367 (2009/06/18)
Photocontrol of a piperidine's Bronsted basicity was achieved by incorporation of a bulky azobenzene group and could be translated into pronounced reactivity differences between ON- and OFF- states in general base catalysis. This enabled successful photomodulation of the catalyst's activity in the nitroaldol reaction (Henry reaction). A modular synthetic route to the photoswitchable catalysts was developed and allowed for preparation and characterization of three azobenzene-derived bases as well as one stilbene-derived base. Solid-state structures obtained by X-ray crystal structure analysis confirmed efficient blocking of the active site in the E isomer representing the OFF-states, whereas a freely accessible active site was revealed for a representative Z isomer in the crystal. To correlate structure with reactivity of the catalysts, conformational dynamics were thoroughly studied in solution by NMR spectroscopy, taking advantage of residual dipolar couplings (RDCs), in combination with comprehensive DFT computational investigations of conformations and proton affinities.
Progressive direct iodination of sterically hindered alkyl substituted benzenes
Stavber, Stojan,Kralj, Petra,Zupan, Marko
, p. 1513 - 1518 (2007/10/03)
Benzene derivatives bearing at least one bulky alkyl group (i-Pr or t-Bu) were selectively and effectively iodinated using elemental iodine activated, by 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor, F-TED