77085-24-6Relevant articles and documents
Desulfurative Chlorination of Alkyl Phenyl Sulfides
Canestrari, Daniele,Lancianesi, Stefano,Badiola, Eider,Strinna, Chiara,Ibrahim, Hasim,Adamo, Mauro F. A.
, p. 918 - 921 (2017/02/26)
The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl2) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides proceeds with high stereospecificity, thus providing a formal entry into enantioenriched chloro-Michael adducts. A mechanism implying the formation of a dichloro-λ4-sulfurane intermediate is proposed.
Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system
Yasuda, Makoto,Yamasaki, Satoshi,Onishi, Yoshiyuki,Baba, Akio
, p. 7186 - 7187 (2007/10/03)
The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate. Copyright
Direct reduction of alcohols: Highly chemoselective reducing system for secondary or tertiary alcohols using chlorodiphenylsilane with a catalytic amount of indium trichloride
Yasuda,Onishi,Ueba,Miyai,Baba
, p. 7741 - 7744 (2007/10/03)
The direct reduction of alcohols using chlorodiphenylsilane as A hydride source in the presence of a catalytic amount of indium trichloride is described. Benzylic alcohols, secondary alcohols, and tertiary alcohols were effectively reduced to give the corresponding alkanes in high yields. A compound bearing both primary and secondary hydroxyl groups was reduced only at the secondary site to afford the primary alcohol after workup with Bu4NF. This system showed high chemoselectivity only for the hydroxyl group while not reducing other functional groups that are readily reduced by standard reducing systems. Thus alcohols bearing ester, chloro, bromo, or nitro groups, which are sensitive to LiAlH4 or Zn/H+, were selectively reduced only at the hydroxyl sites by the chlorodiphenylsilane/InCl3 system. NMR studies revealed the reaction course. The hydrodiphenyl-silyl ether is initially formed and then, with InCl3 acting as a Lewis acid, forms an oxonium complex, which accelerates the desiloxylation with donation of the hydrogen to the carbon.