18002-83-0Relevant articles and documents
Reactivity of Benzylic Carbanions. 10. Rearrangement of the Me3SI Group in 9,9-Bis(trimethylsilyl)- and 9-Alkyl-9-(trimethylsilyl)-10-lithio-9,10-dihydroanthracenes
Daney, Michele,Lapouyade, Rene,Bouas-Laurent, Henri
, p. 5055 - 5062 (1983)
A Me3Si migration has been shown to occur in 9,9-bis(trimethylsilyl)-10-lithio-9,10-dihydroanthracene (C1); the resulting carbanion (C2), protonated by H2O, gives rise exclusively to the cis-9,10-bis(trimethylsilyl)-9,10-dihydroanthracene ((Me3Si)2DHA) in high yield.The same migration was also observed in a series of 9-(trimethylsilyl)-9-alkyl-10-lithio-9,10-dihydroanthracenes (alkyl = Me, Et, i-Pr), which were transformed into a mixture of cis and trans 9,10-disubstituted DHAs (VII, VIII, IX).Experimental evidence was obtained for an intramolecular shift, and the mechanism of the reaction was considered, particularly the possibility of a reversible Me3Si migration (C2 -> C1).The driving force of the Me3Si shift is believed to involve easy formation of pentacoordinated silicon derivatives combined with relief of strain in, and formation of, more stable ion pairs.In light of these results, the rearrangements observed in 9-(trimethylsilyl)-9-deuterio-10-lithio-9,10-dihydroanthracenes were reexamined.A comparison with other well-known R3Si migrations in carbanions, mainly in systems containing heteroatoms, was made, and the structural requirements to observe such reactions in genuine carbanions were delineated; the DHA substrate appears to be well suited for this rearrangement.
Silylated cyclohexadienes as new radical chain reducing reagents: Preparative and mechanistic aspects
Studer, Armido,Amrein, Stephan,Schleth, Florian,Schulte, Tobias,Walton, John C.
, p. 5726 - 5733 (2007/10/03)
Various silylated 1,4-cyclohexadienes are presented as superior tin hydride substitutes for the conduction of various radical chain reductions. Debrominations, deiodinations, and deselenations can be performed using these environmentally benign reagents. Furthermore, Barton - McCombie-type deoxygenations using silylated cyclohexadienes are described. Radical cyclizations, ring expansions, and Giesetype addition reactions with the new tin hydride substitutes are presented. The polymerization of styrene can be regulated using silylated cyclohexadienes. Rate constants for hydrogen atom abstraction from two 1-silyl-cyclohexadienes by primary C-radicals were determined. The effects of the cyclohexadiene substituents on the reaction outcomes are discussed. Finally, qualitative EPR experiments on silyl radical expulsion from silylated cyclohexadienyl radicals are presented.
Silicon Mediated Alkylations in the 9,10-Dihydroanthracene System: A Convenient Synthesis of 9,9-Dialkyl-9,10- Dihydroanthracenes
Rabideau, Peter W.,Dhar,Clawson,Zhan, Zhengyun
, p. 3969 - 3972 (2007/10/02)
A trimethylsilyl (TMS) substituent is used to control the regiochemistry of alkylation in 9,10-dihydroanthracene (9,10-DHA) furnishing 9,9-dialkyl-10-TMS-9,10-DHAs. The TMS group is subsequently removed resulting in the first convenient synthesis of a var