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

62 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

Cite this

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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.\}",

year = "2019",

month = sep,

day = "25",

doi = "10.1021/jacs.9b08634",

language = "English",

volume = "141",

pages = "15450--15455",

journal = "Journal of the American Chemical Society",

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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 - https://www.scopus.com/pages/publications/85072627855

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

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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 -

TEMPO-Me: An Electrochemically Activated Methylating Agent

Abstract

Keywords

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