16537-19-2Relevant articles and documents
A Cyanide-Free Synthesis of Acylcyanides through Ru-Catalyzed C(sp3)-H-Oxidation of Benzylic Nitriles
Eisele, Pascal,Bauder, Michael,Hsu, Shih-Fan,Plietker, Bernd
, p. 689 - 691 (2019/05/07)
A practical method for generation of acylcyanides devoid of any external cyanide sources is presented that relies on a mild Ru-catalyzed selective C?H-oxidation of benzylic nitriles. The starting materials are smoothly generated through condensation of the corresponding carboxylic acid amides using silanes. The obtained acylcyanides can be employed in a plethora of transformation as exemplified to some larger extend in the sequence of C?H-oxidation-Tischenko-rearrangement for the generation of structurally diverse benzoyloxycyanohydrines.
Metal-free carbonylations by photoredox catalysis
Majek, Michal,Von Wangelin, Axel Jacobi
supporting information, p. 2270 - 2274 (2015/02/19)
The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition-metalcatalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners.
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.