TY - JOUR
T1 - Concerning the mechanism of the FeCl3-catalyzed α-oxyamination of aldehydes
T2 - Evidence for a non-SOMO activation pathway
AU - Van Humbeck, Jeffrey F.
AU - Simonovich, Scott P.
AU - Knowles, Robert R.
AU - MacMillan, David W.C.
PY - 2010/7/28
Y1 - 2010/7/28
N2 - The mechanism of a recently reported aldehyde α-oxyamination reaction has been studied using a combination of kinetic, spectrometric, and spectrophotometric techniques. Most crucially, the use of a validated cyclopropane-based radical-clock substrate has demonstrated that carbon-oxygen bond formation occurs predominantly through an enamine activation manifold. The mechanistic details reported herein indicate that, as has been proposed for previously studied alcohol oxidations, complexation between TEMPO and a simple metal salt leads to electrophilic ionic reactivity.
AB - The mechanism of a recently reported aldehyde α-oxyamination reaction has been studied using a combination of kinetic, spectrometric, and spectrophotometric techniques. Most crucially, the use of a validated cyclopropane-based radical-clock substrate has demonstrated that carbon-oxygen bond formation occurs predominantly through an enamine activation manifold. The mechanistic details reported herein indicate that, as has been proposed for previously studied alcohol oxidations, complexation between TEMPO and a simple metal salt leads to electrophilic ionic reactivity.
UR - http://www.scopus.com/inward/record.url?scp=77955779542&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77955779542&partnerID=8YFLogxK
U2 - 10.1021/ja1043006
DO - 10.1021/ja1043006
M3 - Article
C2 - 20608675
AN - SCOPUS:77955779542
SN - 0002-7863
VL - 132
SP - 10012
EP - 10014
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 29
ER -