75730-04-0Relevant articles and documents
Enantioselective Construction of α-Chiral Silanes by Nickel-Catalyzed C(sp3)?C(sp3) Cross-Coupling
Yi, Hong,Mao, Wenbin,Oestreich, Martin
, p. 3575 - 3578 (2019)
An enantioselective C(sp3)?C(sp3) cross-coupling of racemic α-silylated alkyl iodides and alkylzinc reagents is reported. The reaction is catalyzed by NiCl2/(S,S)-Bn-Pybox and yields α-chiral silanes with high enantiocontr
Carboxylation with CO2 via brook rearrangement: Preparation of α-hydroxy acid derivatives
Mita, Tsuyoshi,Higuchi, Yuki,Sato, Yoshihiro
supporting information, p. 14 - 17 (2014/01/23)
In the presence of CsF, a wide range of α-substituted α-siloxy silanes were carboxylated under a CO2 atmosphere (1 atm) via Brook rearrangement. A variety of α-substituents including aryl, alkenyl, and alkyl groups were tolerated to afford α-hydroxy acids in moderate-to-high yields. One-pot synthesis from aldehydes using PhMe2SiLi and CO 2 was also possible, providing α-hydroxy acids without the isolation of an α-hydroxy silane.
On the radical Brook rearrangement. Reactivity of α-silyl alcohols, α- silyl alcohol nitrite esters, and β-haloacylsilanes under radical-forming conditions
Paredes,Alonso
, p. 2292 - 2304 (2007/10/03)
Two alkoxyl radical generation methods, lead tetraacetate treatment of alcohols and photolysis of nitrites, were applied to α-silyl alcohols 21 and to the corresponding nitrites 25 with a view to forming α-silyl alkoxyl radicals 23 and studying their possible radical Brook rearrangement to α- silyloxy carbon radicals 24. LTA treatment of 21 led to their quick and efficient conversion into mixed acetyl-silyl acetals 33 under very mild conditions. Photolysis of α-alkylmonosubstituted α-silyl nitrites 25 to the corresponding aldehydes is considered to proceed through α-silyl alkoxyl radical intermediates 23. A concerted process is, however, proposed for the case of the benzyl nitrites analogues. On the basis of these results, it is postulated that resonance stabilization can have a major influence on the evolution of α-silyl alkoxyl radicals: should this stabilization be possible, they quickly evolve by α-silyl fragmentation; otherwise, they tend to undergo radical Brook rearrangement. It was also found that the radical Brook rearrangement of α-silyl cyclopropyloxyl radicals generated from β- bromoacylsilanes under standard tin-radical conditions is too slow to compete with β-fragmentation.
Synthesis of Acylsilanes from Amides and Esters, and the Selective Oxidation of α-Silyl Alcohols to Aldehydes
Fleming, Ian,Ghosh, Usha
, p. 257 - 262 (2007/10/02)
The acylsilanes 2 can easily be made directly from the dimethylamides 3 by treatment with phenyldimethylsilyllithium.They can also be made in two steps from the esters 4 using 2 equiv. of phenyldimethylsilyllithium followed by oxidation of the disilyl alcohols 5 with PDC.The disilyl alcohols 5 can be used as intermediates in the conversion of esters into aldehydes without recourse to hydride reagents, by monodesilylation, using a Brook rearrangement, followed by oxidation and selective removal of the silyl group, using chromium trioxide in DMSO.
Novel Syntheses of 1,2-Diarylacetylenes and α-Silylalcohols from Acylsilanes Mediated by Ytterbium Metal
Taniguchi, Yuki,Fujii, Nobuto,Makioka, Yoshikazu,Takaki, Ken,Fujiwara, Yuzo
, p. 1165 - 1168 (2007/10/02)
Aromatic acylsilanes such as benzoyltrimethylsilane react with ytterbium metal to give symmetrical 1,2-diarylacetylenes in good yields.Aliphatic acylsilanes are reduced with lanthanoid reagents as Yb metal and SmI2 to afford α-silylalcohols.
The Synthesis of α-Stannyl Silanes and Their Use in the Formation of Alkenes
Barrett, Anthony G. M.,Hill, Jason M.
, p. 3285 - 3288 (2007/10/02)
α-Stannyl-silanes were prepared from aldehydes via α-hydroxy- and α-chloro-silanes.Stannyl-silane 5d was transmetallated using n-butyllithium and the resultant α-lithio-silane condensed with aldehydes to yield alkenes.
GENERATION OF THIOALDEHYDES VIA FLUORIDE INDUCED ELIMINATION OF Α-SILYLDISULFIDES
Krafft, Grant A.,Meinke, Peter T.
, p. 1947 - 1950 (2007/10/02)
A mild, efficient and general method for the generation of reactive thioaldehydes from α-silyldisulfides is described.
THE PREPARATION OF α-HYDROXYORGANOSILANES FROM α-BORYLORGANOSILANE INTERMEDIATES
Larson, Gerald L.,Argueelles, Rafael,Rosario, Osvaldo,Sandoval, Sydia
, p. 15 - 24 (2007/10/02)
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.
