78808-66-9Relevant academic research and scientific papers
SET and exciplex pathways in the photochemical reactions between aromatic ketones and benzylsilane and stannane derivatives
Cermenati, Laura,Freccero, Mauro,Venturello, Paolo,Albini, Angelo
, p. 7869 - 7876 (1995)
The photochemical reaction of α,α,α-trifluoroacetophenone (TFA), benzophenone, and p-cyanoacetophenone with benzyltrimethylsilane in MeCN involves hydrogen transfer from the benzylic position. Desilylation occurs as a minor process only in the case of TFA (but it increases greatly in the presence of MeOH or LiClCO4). The final products result from the statistical recombination of the benzyl and ketyl radicals. Further cases of intramolecular selectivity studied are p-methylbenzyl- and p-methoxybenzyltrimethylsilane (the latter substrate undergoes mainly C-Si bond cleavage in the reaction with TFA) as well as benzyltributylstannane (only destannylation observed with all ketones). Product studies are complemented by the determination of relevant kinetic parameters through steadystate and flash-photolysis experiments. The results are explained in terms of hydrogen transfer proceeding from an exciplex and desilylation from the solvent separated radial ion pair. The latter species predominates when ΔGet -1.
Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine-Directed para and ortho C?H Functionalization
Wu, Yichen,Bouvet, Sébastien,Izquierdo, Susana,Shafir, Alexandr
supporting information, p. 2617 - 2621 (2019/01/04)
Among halogenated aromatics, iodoarenes are unique in their ability to produce the bench-stable halogen(III) form. Earlier, such iodine(III) centers were shown to enable C?H functionalization ortho to iodine via halogen-centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane-directed para C?H benzylation, as well as by developing an efficient C?H coupling with sulfonyl-substituted allylic silanes. Through the combination of the one-shot nature of the coupling event and the iodine retention, multisubstituted arenes can be prepared by sequentially engaging up to three aromatic C?H sites. This type of iodine-based iterative synthesis will serve as a tool for the formation of value-added aromatic cores.
Rhodium-catalyzed silylation and intramolecular arylation of nitriles via the silicon-assisted cleavage of carbon-cyano bonds
Tobisu, Mamoru,Kita, Yusuke,Ano, Yusuke,Chatani, Naoto
supporting information; experimental part, p. 15982 - 15989 (2009/05/16)
A rhodium-catalyzed silylation reaction of carbon - cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from η2-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.
