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Migratory aptitude of substituents on silicon atoms of disilylcarbenes
Author(s) -
Oku Akira,
Miki Toshiyuki,
Ose Yasuyoshi
Publication year - 1996
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199609)9:9<619::aid-poc822>3.0.co;2-w
Subject(s) - diazomethane , chemistry , trimethylsilyl , silylation , ring (chemistry) , silanes , substituent , medicinal chemistry , silicon , photodissociation , alkyl , ketene , stereochemistry , photochemistry , organic chemistry , catalysis , silane
Photolysis of (dimethylphenylsilyl)(trimethylsilyl)diazomethane in t ‐BuOH yielded three different t ‐BuO‐substituted (silylalkyl)silanes. The migratory aptitude of substituents from the silicon atoms to the carbenic center was found to be in the order Ph: Me (on phenyl‐substituted Si):Me (on TMS) = 3·8:1·0:1·0, the opposite of that reported for monosilylcarbenes. The photolysis of (1‐phenyl‐1‐silacyclobutyl)(trimethylsilyl) diazomethane gave two silyl‐substituted silacyclobutanes and one ring‐expanded silacyclopentane. Again, the migratory aptitude of substituents was in the order Ph: ring‐methylene: Me = 4·5:1·4:1·0, showing that the ring shifts faster than Me and also Ph shifts faster than any alkyl substituent.