57137-86-7Relevant academic research and scientific papers
Iron-catalyzed silylcyanation of aldehydes and ketones with silyl cyanide prepared from silane and acetonitrile
Itazaki, Masumi,Nakazawa, Hiroshi
, p. 1054 - 1055 (2005)
Silylcyanation of aldehyde or ketone was performed in a solution involving Et3SiCN produced by photoreaction of Et3SiH with MeCN in the presence of a catalytic amount of Cp(CO)2FeMe (Cp = C 5H5). The iron complex derived from Cp(CO)2FeMe serves as a catalyst both for C-C bond cleavage of MeCN and concomitant Si-C bond formation and for Si-C bond cleavage in silylcyanation. The catalytic reaction mechanism has been discussed. Copyright
Al Lewis acid-catalyzed regiodivergent 1,2-rearrangement of α-siloxy aldehydes: scope and mechanism
Ohmatsu, Kohsuke,Tanaka, Takayuki,Ooi, Takashi,Maruoka, Keiji
experimental part, p. 7516 - 7522 (2009/12/04)
Regiodivergent 1,2-rearrangement of α-siloxy aldehydes bearing α-aryl and α-alkyl substituents into α-siloxy ketones has been realized by using different Al Lewis acid catalyst/solvent systems. The scope of this unprecedented protocol has been investigate
Complete switch of migratory aptitude in aluminum-catalyzed 1,2-rearrangement of differently α,α-disubstituted a-siloxy aldehydes
Ohmatsu, Kohsuke,Tanaka, Takayuki,Ooi, Takashi,Maruoka, Keiji
supporting information; experimental part, p. 5203 - 5206 (2009/04/11)
(Chemical Equation Presented) Control of the migration tendency: The regiodivergent 1,2-rearrangement of asiloxy aldehydes bearing α-aryl and α-alkyl substituents into α-siloxy ketones has been realized by using different aluminum Lewis acid catalyst/solvent systems (see scheme). The scope of this unprecedented protocol has been investigated with various substrates and clearly demonstrates its utility for the selective synthesis of two structural isomers from one substrate.
Catalytic asymmetric rearrangement of α,α-disubstituted α-siloxy aldehydes to optically active acyloins using axially chiral organoaluminum Lewis acids
Ooi, Takashi,Ohmatsu, Kohsuke,Maruoka, Keiji
, p. 2410 - 2411 (2007/10/03)
A catalytic asymmetric rearrangement of α,α-dialkyl-α-siloxy aldehydes has been developed based on the design of a stereochemically defined, axially chiral organoaluminum Lewis acid 3. For instance, treatment of (S,S)-4 (1.1 equiv) with Me3Al in toluene at room temperature for 30 min generated (S,S)-3 (5 mol %), and subsequent reaction with α-siloxy aldehyde 1a (R = CH2Ph) at -20 °C for 12 h resulted in the smooth rearrangement to afford the corresponding α-siloxy ketone 2a (R = CH2Ph) in 96% isolated yield with 87% ee (S). The scope of this unprecedented stereoselective rearrangement has been investigated with representative substrates, in which impressive kinetic resolution of racemic, α,α-disubstituted α-siloxy aldehydes has also been achieved. These results clearly demonstrate the utility of the present approach for the catalytic enantioselective synthesis of various acyloins and tertiary α-hydroxy aldehydes not readily accessible by the previously known asymmetric methodologies. Copyright
An Intramolecular Prins Double Cyclization Catalyzed by Silyl Triflates
Jung, Michael E.,Angelica, Steve,D'Amico, Derin C.
, p. 9182 - 9187 (2007/10/03)
Several intramolecular Prins double cyclizations are reported. The 2-alkyl 5-hepten-1,2-diols and their analogues, 9-11, were prepared and oxidized to the aldehydes 6-8 under Swern conditions. Treatment of these α-hydroxy aldehydes with TBSOTf and a hindered base gave the products of an intramolecular Prins double cyclization, namely the 7-(silyloxy)-2-oxabicyclo[2.2.1]heptanes, 17- 19, in 84-92% yield. These compounds were formed as single diastereomers with only the anti silyl ethers being obtained. The cyclizations occur when five-membered rings are being formed and when the initially formed cation is highly stabilized. Other substrates do not cyclize, e.g., when the α-hydroxy aldehydes 20-22, prepared from 26-28, are treated under similar conditions, none of the corresponding cyclization products, 23-25, were obtained.
