posted on 2014-01-22, 00:00authored byZachary K. Wickens, Kacper Skakuj, Bill Morandi, Robert H. Grubbs
The
aldehyde-selective oxidation of alkenes bearing diverse oxygen groups
in the allylic and homoallylic position was accomplished with a nitrite-modified
Wacker oxidation. Readily available oxygenated alkenes were oxidized
in up to 88% aldehyde yield and as high as 97% aldehyde selectivity.
The aldehyde-selective oxidation enabled the rapid, enantioselective
synthesis of an important pharmaceutical agent, atomoxetine. Finally,
the influence of proximal functional groups on this anti-Markovnikov
reaction was explored, providing important preliminary mechanistic
insight.