Concerning the mechanism of the FeCl3-catalyzed alpha-oxyamination of aldehydes: evidence for a non-SOMO activation pathway.
The mechanism of a recently reported aldehyde alpha-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.
Van Humbeck
Jeffrey F
JF
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, USA.
Simonovich
Scott P
SP
Knowles
Robert R
RR
MacMillan
David W C
DW
D000447:Aldehydes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000737:chemistry; D003521:Cyclopropanes / Q000737:chemistry; D004563:Electrochemistry; D005290:Ferric Compounds / Q000737:chemistry*; D007536:Isomerism; D010100:Oxygen / Q000737:chemistry; D012997:Solvents / Q000737:chemistry
D000447:Aldehydes; D002712:Chlorides; D003497:Cyclic N-Oxides; D003521:Cyclopropanes; D005290:Ferric Compounds; D012997:Solvents; C030797:cyclopropane; D010100:Oxygen; C024555:ferric chloride; C003959:TEMPO