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Silylene Reactions with Buta-1,3-diynes: Cycloadditions, Insertions, and Rearrangements

✍ Scribed by Detlev Ostendorf; Lars Kirmaier; Wolfgang Saak; Heinrich Marsmann; Manfred Weidenbruch

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
420 KB
Volume
1999
Category
Article
ISSN
1434-1948

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✦ Synopsis

Di-tert-butylsilylene, generated by photolysis of hexa-tert-gives the corresponding alkynylsilirenes 14 and 15, respectively. Photolysis of 1 or 2 in the presence of (Me 3 Si-butylcyclotrisilane 1 or 1,1-di-tert-butyl-trans-2,3-dimethylsilirane (2), reacts with the 1,3-diyne (tBu-CϵC-) 2 9 to CϵC-) 2 16 yields the dialkynylsilane 17 which, on further reaction with 2, yields the 2,5-disilabicyclo[2.2.0]hexa-1(6),3-furnish the dialkynylsilane 11 via the isolable alkynylsilirene 10. Photolysis of excess 1 in the presence of 9 furnishes the diene (18). Irradiation of 3 in the presence of 16 affords the cis-and trans-isomeric 1,3-dimethylene-2,4-disila-C-C linked 2,2Ј-disilirene 12 which, upon prolonged irradiation, rearranges to the 2,5-disilabicyclo[2.2.0]hexa-cyclobutane derivatives cis-21 and trans-21, presumably via a 1-silaallene intermediate. The structures of 12, 15, 18, cis-1(6),3-diene (13). Treatment of 9 with diarylsilylenes, formed by irradiation of hexamethyl-2,2-dimesityltrisilane (3) or 21, and trans-21 have been determined by X-ray crystallography. hexamethyl-2,2-bis(2,4,6-triisopropylphenyl)trisilane (4),

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