- The Insertion Reaction of 1CH2 into the Silicon-Carbon Bond
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Singlet methylene reacts with 1,1-dimethylsilacyclobutane to yield as well as the expected products formed by C-H insertion some 1,1-dimethylsilacyclopentane which strongly suggests that it can insert in the silicon-carbon bond.
- Frey, H. Monty,Walsh, Robin,Watts, Ivy M.
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p. 284 - 285
(2007/10/02)
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- Carbanion Rearrangements of ω-Phenyl-ω-(trimethylsilyl)alkyllithium Compounds: Intramolecular Reactions of Benzyltrimethylsilanes with a Carbon-Lithium Bond
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ω-Phenyl-ω-(trimethylsilyl)alkyllithium compounds show four out of five theoretically conceivable possibilities for intramolecular stabilization depending on the solvent and on the chain length n.While transmetalation of a methyl group at the silicon atom by a 1,(n+2) proton transfer is observed in any case, the intramolecular 1,n shift of the benzylic proton does only take place with n >/= 4.The main reaction, however for n = 3 and 4 only, is represented by the 1,n trimethylsilyl shift via a cyclic ate complex as an intermediate which partly splits off methyllithium yielding the corresponding silacycloalkane derivatives.In going from diethyl ether to THF as the solvent, the silyl shifts are more accelerated than the proton shifts.In no case, however, a Grovenstein-Zimmermann rearrangement involving phenyl migration took place.Degenerate silyl shifts starting from α-deuterated ω-(trimethylsilyl)alkyllithium compounds could not be detected either.Only by introduction of a second trimethylsilyl group into the 3 position a 1,3-(C -> C)-trimethylsilyl shift is initiated again.
- Maercker, Adalbert,Stoetzel, Reinhard
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p. 1695 - 1706
(2007/10/02)
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