66235-32-3Relevant academic research and scientific papers
THE PREPARATION OF α-HYDROXYORGANOSILANES FROM α-BORYLORGANOSILANE INTERMEDIATES
Larson, Gerald L.,Argueelles, Rafael,Rosario, Osvaldo,Sandoval, Sydia
, p. 15 - 24 (1980)
The generation of α-silyl-α-borylmethane derivatives as intermediates and their oxidation to α-hydroxyorganosilanes is reported.The formation of the intermediate α-silyl-α-borylmethane derivatives is via the type I transfer reaction of organoboranes with either (trimethylsilyl)bromomethyllithium and (phenyldimethylsilyl)chloromethyllithium in THF or in some cases hexane.
Synthetic utility and mechanistic studies of the aliphatic reverse brook rearrangement
Linderman, Russell J.,Ghannam, Ameen
, p. 2392 - 2398 (2007/10/02)
The aliphatic reverse Brook rearrangement has been examined in detail. Transmetalation of [α-[(trialkylsilyl)-oxy]alkyl]trialkylstannanes occurs via a complex equilibrium favoring the most stable carbanion. The aliphatic reverse Brook rearrangement is driven forward by the rapid migration of silicon from O to C in a transient α-silyloxy carbanion due to the formation of the more stable lithium alkoxide. Cross-over experiments have shown that the rearrangement is an intramolecular process while incorporation of a radical trap revealed that the rearrangement does not involve radical intermediates. Studies of configurationally fixed stannanes derived from 4-tert-butylcyclohexanone concluded that the rearrangement occurs with retention of configuration. Preparation and reverse Brook rearrangement of optically active (S)-[α-[(trimethylsilyl)oxy]-hexyl]tributylstannane (98% ee) provided 1-(trimethylsilyl)hexanol in 97% ee. The synthetic utility of this method for the preparation of a variety of (α-hydroxyalkyl)trialkylsilanes from aldehydes has also been demonstrated.
Synthesis of (α-Hydroxyalkyl)trialkylsilanes via a Reverse Brook Rearrangement
Linderman, Russell J.,Ghannam, Ameen
, p. 2878 - 2880 (2007/10/02)
The transmetalation and rearrangement of trialkylstananes have been achieved, providing a method for the direct conversion of several aldehydes and cyclohexanone into (α-hydroxyalkyl)trialkylsilanes in reasonable yields.
