Diadamantylsilylene and its stereochemistry of addition

Article abstract of DOI:10.1021/ja00004a031

Lithium-induced dehalogenation assisted by ultrasonic irradiation of diadamantyldiiodosilane in the presence of olefins and alkynes leads to high yields of 1,1 -diadamantylsiliranes and 1,1 -diadamantylsilirenes, respectively. The siliranes are precursors for the efficient thermal and photochemical generation of diadamantylsilylene (Ad₂Si:). The addition of thermally generated Ad₂Si: to cis- and trans-2-butene and -3-hexene is totally stereospecific, implying reaction from a singlet electronic state of the silylene. Photoisomerization of cis- and trans-1,1 -diadamantylsiliranes complicates the study of the stereochemistry of addition of photogenic Ad₂Si:, but again a high degree of stereospecificity is observed.