43226-07-9Relevant articles and documents
Metallaphotoredox-Catalyzed Cross-Electrophile Csp3-Csp3 Coupling of Aliphatic Bromides
Smith, Russell T.,Zhang, Xiaheng,Rincón, Juan A.,Agejas, Javier,Mateos, Carlos,Barberis, Mario,García-Cerrada, Susana,De Frutos, Oscar,Macmillan, David W. C.
supporting information, p. 17433 - 17438 (2019/01/04)
A strategy for the installation of small alkyl fragments onto pharmaceutically relevant aliphatic structures has been established via metallaphotoredox catalysis. Herein, we report that tris(trimethylsilyl)silanol can be employed as an effective halogen abstraction reagent that, in combination with photoredox and nickel catalysis, allows a generic approach to Csp3-Csp3 cross-electrophile coupling. In this study, we demonstrate that a variety of aliphatic drug-like groups can be successfully coupled with a number of commercially available small alkyl electrophiles, including methyl tosylate and strained cyclic alkyl bromides. Moreover, the union of two secondary aliphatic carbon centers, a long-standing challenge for organic molecule construction, has been accomplished with a wide array of structural formats. Last, this technology can be selectively merged with Csp2-Csp3 aryl-alkyl couplings to build drug-like systems in a highly modular fashion.
A direct and stereoretentive synthesis of amides from cyclic alcohols
Mondal, Deboprosad,Bellucci, Luca,Lepore, Salvatore D.
, p. 7057 - 7061 (2012/01/03)
Chlorosulfites prepared in situ using thionyl chloride react with nitrile complexes of titanium(IV) fluoride to give a one-pot conversion of alcohols into amides. For the first time, amides are obtained from cyclic alcohols with stereoretention. Critical to the design of these new TiIV reactions has been the use of little-explored TiIV nitrile complexes that are thought to chelate chlorosulfites in the transition state tocreate a carbocation that is rapidly captured by the nitrile nucleophile through a front-side attack mechanism.