112947-62-3Relevant academic research and scientific papers
Synthesis of (α-Hydroxyalkyl)trialkylsilanes via a Reverse Brook Rearrangement
Linderman, Russell J.,Ghannam, Ameen
, p. 2878 - 2880 (1988)
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.
Enantioconvergent Cross-Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes
Schwarzwalder, Gregg M.,Matier, Carson D.,Fu, Gregory C.
, p. 3571 - 3574 (2019)
Metal-catalyzed enantioconvergent cross-coupling reactions of alkyl electrophiles are emerging as a powerful tool in asymmetric synthesis. To date, high enantioselectivity has been limited to couplings of electrophiles that bear a directing group or a pro
Preparation of alcohols from alkenes via the homologation of boronates with (trimethylsilyl)diazomethane
Goddard, Jean-Philippe,Le Gall, Thierry,Mioskowski, Charles
, p. 1455 - 1456 (2007/10/03)
(Matrix presented) Alkylcatecholboranes obtained from alkenes were converted to the corresponding alkylmethanols by reaction with (trimethylsilyl)diazomethane followed by oxidation and treatment with fluoride.
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.
