UNIQUE REACTIVITY OF A DIPHENYLDISILANE UNIT INCORPORATED IN A BICYCLIC RING SYSTEM: GENERATION OF A DISILANYLLITHIUM VIA THE SILICON-PHENYL BOND CLEAVAGE WITH LITHIUM
Ключевые слова:
bicyclic disilane, disilanyllithium, methylene tethers, silicon-carbon bond cleavage, silyllithium, Calas-type reactionАннотация
A bicyclic diphenyldisilane bearing two tetramethylene tethers reacts with lithium to form predominantly the disilanyllithium as a result of Si–CPh bond fission, while the pentamethylene homolog undergoes, the ordinary Si–Si bond cleavage to afford the expected phenylsilyllithium. The compressed Si–Si bond incorporated in the bicyclic ring system maybe kinetically stabilized ("compression effect"), resulting in the unusual Si–C bond fission. When the
reaction is carried out in the presence of chlorotrimethylsilane, the Calas-type reaction takes place on the phenyl rings. This result suggests that the electron transfer to the phenyl group is the primary process in these bicyclic disilanes followed by the Si–Si or Si–C bond cleavage to afford the corresponding silyllithium species.
How to Cite
Tsuji, H.; Toshimitsu, A.; Tamao, K. Chem. Heterocycl. Compd. 2001, 37, 1369. [Khim. Geterotsikl. Soedin. 2001, 1500.]
For this article in the English edition, see DOI https://doi.org/10.1023/A:1017947100644
