Direct conversion of carbonyl compounds into organic halides: indium(III) hydroxide-catalyzed deoxygenative halogenation using chlorodimethylsilane.
The reaction of carbonyls and chlorodimethylsilane was effectively catalyzed by indium(III) hydroxide and afforded the corresponding deoxygenative chlorination products, in which the carbonyl carbon accepted two nucleophiles (H and Cl) with releasing oxygen. Only In(OH)3 catalyzed the reaction, and typical Lewis acids such as TiCl4, AlCl3, and BF3.OEt2 showed no catalytic activity. The reaction mechanism of this deoxygenative chlorination includes initial hydrosilylation followed by chlorination. Other nucleophiles such as allyl or iodine were available for this methodology. The moderate Lewis acidity of indium catalyst enabled chemoselective reaction, and therefore ester, nitro, cyano, or halogen groups were not affected during the reaction course.
Onishi
Yoshiyuki
Y
Department of Molecular Chemistry and Handai Frontier Research Center, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Ogawa
Daigo
D
Yasuda
Makoto
M
Baba
Akio
A