2. 2. 1.

Article abstract of DOI:10.1246/bcsj.56.2784

A new class of bicyclic compounds containing a single silicon atom at the bridge, 2-exo- and endo-substituted 2-methyl-2-silabicyclo left bracket 2. 2. 1 right bracket heptanes, have been prepared from the corresponding 3-cyclopentenylmethylhydrosilane by the intramolecular hydrosilylation catalyzed by chloroplatinic acid, and their structures were unequivocally assigned by **1H and **1**3C NMR spectra. Dramatic crossover from inversion to retention was found in the phenylation of chlorosilanes with phenyllithium and phenylmagnesium bromide in ether. Regio- and stereoselective insertion of dichlorocarbene generated from phenyl(bromodichloromethyl)mercury, or from chloroform and sodium hydroxide in the presence of a phase transfer catalyst, into C//(//6//)-H//(//e//x//o//) bond of 2-silanorbornanes is observed.