88257-40-3Relevant academic research and scientific papers
Scope and mechanism of the intermolecular addition of aromatic aldehydes to olefins catalyzed by Rh(I) olefin complexes
Roy, Amy H.,Lenges, Christian P.,Brookhart, Maurice
, p. 2082 - 2093 (2007/10/03)
Rhodium (I) bis-olefin complexes Cp*Rh(VTMS)2 and Cp?Rh(VTMS)2 (Cp* = C5Me5, Cp? = C5-Me4CF3, VTMS = vinyl trimethylsilane) were found to catalyze the addition of aromatic aldehy
Reaction of acylsilanes with sulfur ylides. Selective formation of silyl enol ethers or β-ketosilanes
Nakajima, Tadashi,Segi, Masahito,Sugimoto, Fumitosi,Hioki, Reiko,Yokota, Seiko,Miyashita, Kiyoshi
, p. 8343 - 8358 (2007/10/02)
The reaction of acylsilanes with sulfur ylides in THF results in the formation of the corresponding silyl enol ethers or β-ketosilanes. The relative ratio of these products varies with the ylide conditions and the stability of ylide used. It is noteworthy that silyl enol ethers were formed under the salt-free ylide conditions, and that β-ketosilanes were yielded in the presence of soluble inorganic salts in THF, selectively. The formation of both products would be interpreted in terms of the anionotropic and cationotropic rearrangements of silyl group in the reaction intermediate.
A regiodefined synthesis of α-trimethylsilyl ketones catalyzed by rhodium(I) hydride complex
Sato, Susumu,Matsuda, Isamu,Izumi, Yusuke
, p. 71 - 88 (2007/10/02)
Regiodefined synthesis of α-trimethylsilyl ketones is attained by one of three different routes: isomerization of β-trimethylsilyl allyl alcohols (route A), isomerization of β'-trimethylsilyl allyl alcohols (route B), and dehydrogenation of β-trimethylsil
A New Synthesis of β-Keto Phosphonates and β-Keto Silanes
Sampson, Paul,Hammond, Gerald B.,Wiemer, David F.
, p. 4342 - 4347 (2007/10/02)
A new preparation of β-keto phosphonates from α-bromo ketones, by reaction of dialkyl chlorophosphate electrophiles with the dilithiated derivative of the bromo ketone, is described.This umpolung approach is complementary to the classical Arbuzov synthesis in two important ways.It extends the range of possible ketone substrates, allowing use of secondary α-halo ketones or α-bromo ketones where the Arbuzov reaction often fails.It also extends the variety of phosphonates available, by allowing, for example, the direct preparation of bis-(trifluoroethyl)phosphonates.These fluoroalkyl phosphonates are not readily available via the Arbuzov reaction,because tris(trifluoroethyl) phosphite is only weakly nucleophilic.From our efforts to employ (trialkylsiloxy)vinyl bromides and n-butyllithium to generate an intermediate vinyllithium reagent, in place of forming the lithium enolate and using tert-butyllithium, a facile migration of trialkylsilyl groups from oxygen to the α-carbon has been discovered.This has been exploited in the development of a new route from α-bromo ketones to α-trialkylsilyl ketones.
α-Trialkylsilylketones from α-Bromoketones: Utilization of a 1,3-O to C Silyl Migration
Sampson, Paul,Wiemer, David F.
, p. 1746 - 1747 (2007/10/02)
A new route from α-bromoketones to α-trialkylsilylketones has been developed which demonstrates the viability of halogen-metal exchange vis-a-vis nucleophilic attack at silicon, even with the unhindered trimethylsilyl group.
A FACILE SYNTHESIS OF α-TRIMETHYLSILYL KETONES AND THEIR REGIOSPECIFIC REARRANGEMENT TO TRIMETHYLSILY ENOL ETHERS
Sato, Susumu,Matsuda, Isamu,Izumi, Yusuke
, p. 3855 - 3858 (2007/10/02)
The rhodium catlyzed isomerization of β-trimethylsilylallyl alcohols has been successfully applied for the stepwise and selective synthesis of α-trimethylsilyl ketones and trimethylsilyl enol ethers.
