D. Seyferth, H. Shih, J. Dubac
Mar 16, 1973
Citations
0
Influential Citations
30
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Reaction of n-butylmagnesium bromide with a 1/1 cis/trans mixture of 1,3-dimethyl-1-chloro-1-silacyclobutane gave a 1/1 cis/trans mixture of 1,3-dimethyl-1-n-butyl-1-silacyclobutane and reaction of n-butyllithium with a 4/1 cis/trans mixture of 1,3-dimethyl-1-tert-butoxy-1-silacyclobutane resulted in a 4/1 mixture of the (presumed) cis and trans isomers of 1,3-dimethyl-1-n-butyl-1-silacyclobutane. Both of these isomer mixtures were treated with phenyl(bromodichloromethyl)mercury in benzene at 80° to give a mixture of the β CH dichlorocarbene insertion product. 1,3-dimethyl-1-n-butyl-3-(dichloromethyl)-1-silacyclobutane (major product) and the SiC insertion product, 2,2-dichloro-1,4-dimethyl-1-n-butyl-1-silacyclopentane. The NMR spectra of these products showed that both were formed as a mixture of cis and trans isomers, with the isomer ratios being very similar to those of the starting silacyclobutane. It was concluded that these stereoselective CCl2 insertion processes proceed with overall retention of configuration.