630-95-5Relevant articles and documents
(2-Ethylhexyl)sodium: A Hexane-Soluble Reagent for Br/Na-Exchanges and Directed Metalations in Continuous Flow
Annapureddy, Rajasekar Reddy,Harenberg, Johannes H.,Hoefer, Carla A.,Knochel, Paul,Weidmann, Niels,Wiegand, Alexander J.
supporting information, p. 14296 - 14301 (2021/05/07)
We report the on-demand generation of hexane-soluble (2-ethylhexyl)sodium (1) from 3-(chloromethyl)heptane (2) using a sodium-packed-bed reactor under continuous flow conditions. Thus, the resulting solution of 1 is free of elemental sodium and therefore suited for a range of synthetic applications. This new procedure avoids the storage of an alkylsodium and limits the handling of metallic sodium to a minimum. (2-Ethylhexyl)sodium (1) proved to be a very useful reagent and undergoes in-line Br/Na-exchanges as well as directed sodiations. The resulting arylsodium intermediates are subsequently trapped in batch with various electrophiles such as ketones, aldehydes, Weinreb-amides, imines, allyl bromides, disulfides and alkyl iodides. A reaction scale-up of the Br/Na-exchange using an in-line electrophile quench was also reported.
The absolute configuration of simple aliphatic alcohols through a chemical/computational approach: triarylether derivatives of (+)-endo-2-norborneol as a case study
Mazzeo, Giuseppe,Scafato, Patrizia,Superchi, Stefano,Rosini, Carlo
body text, p. 2435 - 2437 (2010/03/03)
The reliable determination of the absolute configuration of (+)-endo-2-norborneol 1, chosen as a representative case of simple aliphatic UV-vis transparent alcohols, was obtained by transforming this compound in its 1-naphthyl-diphenylmethyl ether 5 whose
Palladium-catalyzed arylation of α,α-disubstituted arylmethanols via cleavage of a C-C or a C-H bond to give biaryls
Terao, Yoshito,Wakui, Hiroyuki,Nomoto, Michiyo,Satoh, Tetsuya,Miura, Masahiro,Nomura, Masakatsu
, p. 5236 - 5243 (2007/10/03)
The palladium-catalyzed arylation of α,α-disubstituted arylmethanols with aryl halides proceeds not only via C-H bond cleavage at the ortho-position, but also via cleavage of the sp2-sp3 C-C bond with the liberation of ketones (β-carbon elimination) to give the corresponding biaryls. Both reactions appear to occur through common arylpalladium(II) alcoholate intermediates. The results of systematic studies with respect to which C-C or C-H bond is preferentially cleaved in the arylation are reported. Among the important findings is the selective elimination of ortho-substituted aryl groups even from aryl(diphenyl)methanols due to steric reasons. Thus, various biaryls having ortho-substituents can be produced efficiently by treatment of the corresponding aryl(diphenyl or dimethyl)methanols with aryl bromides and chlorides.