TEMPO-Me: An Electrochemically Activated Methylating Agent

Philip L. Norcott; Chelsey L. Hammill; Benjamin B. Noble; Johnathon C. Robertson; Angus Olding; Alex C. Bissember; Michelle L. Coote

doi:10.1021/jacs.9b08634

TEMPO-Me: An Electrochemically Activated Methylating Agent

Philip L. Norcott, Chelsey L. Hammill, Benjamin B. Noble, Johnathon C. Robertson, Angus Olding, Alex C. Bissember, Michelle L. Coote

Research output: Contribution to journal › Article › peer-review

55 Citations (Scopus)

Abstract

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 S_N2 mechanism, with a strength comparable to the trimethyloxonium cation. A protocol is developed for the electrochemical methylation of aromatic acids using TEMPO-Me.

Original language	English
Pages (from-to)	15450-15455
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	141
Issue number	38
DOIs	https://doi.org/10.1021/jacs.9b08634
Publication status	Published - 25 Sept 2019
Externally published	Yes

Keywords

methylating agents
TEMPO polymers
1-methoxy-2,2,6,6-tetramethylpiperidine (TEMPO−Me)
electrochemical stimulus
SN2 mechanism
electrochemical methylation

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10.1021/jacs.9b08634Licence: In Copyright

http://hdl.handle.net/1885/209107Licence: In Copyright

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title = "TEMPO-Me: An Electrochemically Activated Methylating Agent",

abstract = "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.",

keywords = "methylating agents, TEMPO polymers, 1-methoxy-2,2,6,6-tetramethylpiperidine (TEMPO−Me), electrochemical stimulus, SN2 mechanism, electrochemical methylation",

author = "Norcott, {Philip L.} and Hammill, {Chelsey L.} and Noble, {Benjamin B.} and Robertson, {Johnathon C.} and Angus Olding and Bissember, {Alex C.} and Coote, {Michelle L.}",

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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

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TEMPO-Me: An Electrochemically Activated Methylating Agent

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Keywords

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