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
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.
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.
