Ion-cyclotron resonance studies of alkylsilyl ions. VI. The reactions of 2,2-dimethylpropan-1-ol and 1-methoxy-2,2-dimethylpropane with the trimethylsilyl cation

1980 ◽  
Vol 33 (5) ◽  
pp. 1143 ◽  
Author(s):  
VC Trenerry ◽  
IA Blair ◽  
JH Bowie
Keyword(s):  
Cyclotron Resonance ◽  
Hydride Transfer ◽  
The Other ◽  
Acceptor Site ◽  
Ion Cyclotron Resonance ◽  
Trimethylsilyl Cation ◽  
Ion Cyclotron

The trimethylsilyl cation forms 1 : 1 adducts with both 2,2- dimethylpropan-1-ol and 1-methoxy-2,2-dimethylpropane, with both adducts eliminating C5H10 by (at least) two mechanisms. One mechanism involves a 1,2-hydride transfer from the carbon α to oxygen to the oxygen acceptor site; the other a 1,4-transfer from a γ-carbon substituent.

Ion-Cyclotron Resonance Studies of Alkylsilyl Ions. I. The Reactions Between Alcohols and the Trimethylsilyl Cation

1979 ◽  
Vol 32 (1) ◽  
pp. 59 ◽  
Author(s):  
IA Blair ◽  
G Phillipou ◽  
JH Bowie
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Cyclotron Resonance ◽  
Nucleophilic Attack ◽  
Ion Cyclotron Resonance ◽  
Trimethylsilyl Cation ◽  
Ion Cyclotron ◽  
Decomposition Pathway ◽  
Membered Transition State

Nucleophilic attack of an alcohol (ROH) at the electrophilic silicon centre of the trimethylsilyl cation (Me3Si+) produces the 1 : 1 adduct Me3-O+(H)R(1). The adduct may fragment by loss of methane to yield Me2Si+-O-R; and this elimination is most pronounced when R = Me. When R ≥ C2H5, the major decomposition pathway of (1) involves elimination of the alkene [R-H] to produce Me3Si-O+H2, which may undergo further reaction with the neutral alcohol to reform (1). The proton transfer which accompanies the elimination of [R- H] from (1) originates predominantly from C2 of the alcohol; this suggests the intermediacy of a four-membered transition state in this reaction.

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