TY - JOUR
T1 - TEMPO-Me
T2 - An Electrochemically Activated Methylating Agent
AU - Norcott, Philip L.
AU - Hammill, Chelsey L.
AU - Noble, Benjamin B.
AU - Robertson, Johnathon C.
AU - Olding, Angus
AU - Bissember, Alex C.
AU - Coote, Michelle L.
PY - 2019/9/25
Y1 - 2019/9/25
N2 - Bench- and air-stable 1-methoxy-2,2,6,6-tetramethylpiperidine (TEMPO-Me) is relatively unreactive at ambient temperature in the absence of an electrochemical stimulus. In this report, we demonstrate that the one-electron electrochemical oxidation of TEMPO-Me produces a powerful electrophilic methylating agent in situ. Our computational and experimental studies are consistent with methylation proceeding via a SN2 mechanism, with a strength comparable to the trimethyloxonium cation. A protocol is developed for the electrochemical methylation of aromatic acids using TEMPO-Me.
AB - Bench- and air-stable 1-methoxy-2,2,6,6-tetramethylpiperidine (TEMPO-Me) is relatively unreactive at ambient temperature in the absence of an electrochemical stimulus. In this report, we demonstrate that the one-electron electrochemical oxidation of TEMPO-Me produces a powerful electrophilic methylating agent in situ. Our computational and experimental studies are consistent with methylation proceeding via a SN2 mechanism, with a strength comparable to the trimethyloxonium cation. A protocol is developed for the electrochemical methylation of aromatic acids using TEMPO-Me.
KW - methylating agents
KW - TEMPO polymers
KW - 1-methoxy-2,2,6,6-tetramethylpiperidine (TEMPO−Me)
KW - electrochemical stimulus
KW - SN2 mechanism
KW - electrochemical methylation
UR - http://www.scopus.com/inward/record.url?scp=85072627855&partnerID=8YFLogxK
UR - http://purl.org/au-research/grants/ARC/FL170100041
UR - http://purl.org/au-research/grants/ARC/CE140100012
U2 - 10.1021/jacs.9b08634
DO - 10.1021/jacs.9b08634
M3 - Article
C2 - 31483627
AN - SCOPUS:85072627855
SN - 0002-7863
VL - 141
SP - 15450
EP - 15455
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 38
ER -