369386-28-7Relevant academic research and scientific papers
Unusually accelerated silylmethyl transfer from tin in stille coupling: Implication of coordination-driven transmetalation
Itami,Kamei,Yoshida
, p. 8773 - 8779 (2007/10/03)
The palladium-catalyzed cross-coupling reaction of 2-PyMe2SiCH2SnBu3 with aryl iodide (Ar-I) exclusively produced the 2-PyMe2SiCH2 transferred product 2-PyMe2SiCH2Ar. The relative transfer ability of organic group from tin was found to be 2-PyMe2SiCH2 ? Ph > Me > Bu ? PhMe2SiCH2, which implies the beneficial pyridyl-to-palladium coordination effect. Thus, the transfer of the silylmethyl group from tin to palladium was remarkably accelerated by simply appending the 2-pyridyl group on silicon. The pyridyl-to-palladium coordination was validated in the palladium(II) complex 2-PyMe2SiCH2PdClPPh3 by 1H NMR and X-ray crystal structure analysis. The cross-coupling product was used for further transformations. The C - Si oxidation of the cross-coupling product 2-PyMe2SiCH2Ar afforded ArCH2OH in high yield. The fluoride ion-catalyzed 1,2-addition of 2-PyMe2SiCH2Ar to carbonyl compound (RR′C=O) gave ArCH2C(OH)RR′ in high yield.
