Arynes, generated in situ from 2-(trimethylsilyl)aryl triflate and a fluoride ion, were found to insert into a silicon-silicon bond of cyclic disilanes in the presence of a catalytic amount of a palladium-tert-alkyl isocyanide complex to afford diverse benzo-annulated disilacarbocycles straightforwardly in modest to high yields.
The reactions of pure cis-and trans-3,4benzo-1,2-di(tert-butyl)-1,2-dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) with oxygen in the presence of AIBN proceeded stereospecifically to give the respective siloxanes. The palladium-catalyzed reactions of 1a and 1b with phenylacetylene and 1-hexyne produced stereospecifically cis-and trans-5,6-benzo-1,4-disilacyclohexa-2,5dienes.
The reaction of cis- and trans-3,4-benzo-1,2-di(tert-butyl)-1,2-dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) with chlorine gas in carbon tetrachloride proceeded stereospecifically to
give meso- and rac-1,2-bis[(tert-butyl)chloromethylsilyl]benzene (2a and 2b, respectively).
The condensation of 2a and 2b with lithium and sodium produced a mixture of cis- and
trans-benzodisilacyclobutene 1a and 1b, respectively. The reaction of 1a and 1b with
molecular oxygen proceeded with high stereospecificity to give the respective cis- and trans-4,5-benzo-2-oxa-1,3-disilacyclopent-4-ene. The palladium-catalyzed reactions of 1a and 1b
with phenylacetylene, 1-hexyne, tert-butylacetylene, phenyl-1-propyne, and diphenylacetylene
proceeded in a stereospecific fashion to give the corresponding 5,6-benzo-1,4-disilacyclohexa-2,5-diene derivatives. Similar reactions of 1a and 1b with trimethylsilylacetylene, dimethylphenylsilylacetylene, and mesitylacetylene gave stereospecifically the erythro- and threo-1,2-bis(silyl)benzene derivatives. The structure of trans-5,6-benzo-1,4-di(tert-butyl)-1,4-dimethyl-2-phenyl-1,4-disilacyclohexa-2,5-diene was determined by single-crystal X-ray
crystallography.
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