18032-47-8Relevant academic research and scientific papers
A flow microreactor system enables organolithium reactions without protecting alkoxycarbonyl groups
Nagaki, Aiichiro,Kim, Heejin,Moriwaki, Yuya,Matsuo, Chika,Yoshida, Jun-Ichi
supporting information; experimental part, p. 11167 - 11177 (2010/11/04)
A flow microreactor system consisting of micromixers and microtube reactors provides an effective tool for the generation and reactions of aryllithiums bearing an alkoxycarbonyl group at para-, meta-, and ortho-positions. Alkyl p- and m-lithiobenzoates were generated by the I/Li exchange reaction with PhLi. The Br/Li exchange reactions with sBuLi were unsuccessful. Subsequent reactions of the resulting aryllithiums with electrophiles gave the desired products in good yields. On the other hand, alkyl o-lithiobenzoates were successfully generated by the Br/ Li exchange reaction with sBuLi. Subsequent reactions with electrophiles gave the desired products in good yields.
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.
