Synthesis and some reactions of dibutyltin (S)- and (R)-camphorsulfonyl hydrides.
The synthesis and physical properties of dibutyltin (S)-camphorsulfonyl hydride (1) and dibutyltin (R)-camphorsulfonyl hydride (2), and diphenyltin (S)-camphorsulfonyl hydride (3) as well as that of their organotin precursors are described. Their reactivity with different amines as triethylamine, morpholine and pyridine has been compared with other mixed hydrides as dibutyltin chloride hydride, dibutyltin acetate hydride and dibutyltin dihydride. It has been studied also the possibility of using of dibutyltin (R)- or (S)-camphorsulfonyl hydrides for the stereoselective reduction of different ketones as acetophenone, menthon, camphor and cyclopropyl-(4-metoxyphenyl)-methanone. The reduction of acetophenone with studied camphorsulfonyl hydrides carried out in benzene at room temperature afforded 1-phenylethanol with relatively low enantioselectivity. Addition of 10 equiv. of MnCl(2)*4H(2)O or ZnCl(2) to the reduction mixture involving dibutyltin (S)-camphorsulfonyl hydride (1) and acetophenone and carried out in methanol and tetrahydrofuran, respectively, resulted in remarkable increase in enantioselectivity. The comparative kinetic studies of reduction of acetophenone by different hydrides proved that dibutyltin camphorsulfonyl hydride is significantly more reactive in comparison with dibutyltin chloro hydride and dibutyltin acetate hydride. Analogous results have been obtained from kinetic studies for different tin hydrides with chosen amines. The outcome of these studies supported by theoretical calculations led to the conclusion that the order of reactivity of the studied hydrides correlates with the rate of their homolytic decomposition at room temperature.
Kinart
Wojciech J
WJ
Department of Organic Chemistry, University of Lodz, 90-136 Lodz, Poland. ckinart@uni.lodz.pl
Kinart
Cezary M
CM
Kozak
Monika
M
Kinart
Andrzej
A
Sendecki
Marcin
M
Matczak
Piotr
P
D002164:Camphor / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009947:Organotin Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D007659:Ketones; D009947:Organotin Compounds; C546232:dibutyltin camphorsulfonyl hydride; C546233:diphenyltin camphorsulfonyl hydride; C056189:di-n-butyltin; D002164:Camphor