Hidden Boron Catalysis: A Cautionary Tale on TMEDA Inhibition

Julie Macleod; Andrew D. Bage; Leonie M. Meyer; Stephen P. Thomas

doi:10.1021/acs.orglett.4c03591

Hidden Boron Catalysis: A Cautionary Tale on TMEDA Inhibition

Julie Macleod, Andrew D. Bage, Leonie M. Meyer, Stephen P. Thomas^*

^*Corresponding author for this work

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

Abstract / Description of output

Hidden boron catalysis plagues catalyzed hydroboration reactions, with the “catalyst” acting to mediate the decomposition of HBpin/HBcat to BH₃ which is the actual (hidden) catalyst. N,N,N′,N′-Tetramethylethylenediamine (TMEDA) has been used to identify hidden boron catalysis through trapping/inhibition. Kinetic analyses showed that TMEDA inhibition is only applicable below 60 °C and that other amine traps are likewise ineffective. Awareness of this temperature limitation reveals widespread hidden catalysis in previous methods and should limit future false negative tests.

Original language	English
Pages (from-to)	9564-9567
Number of pages	4
Journal	Organic letters
Volume	26
Issue number	44
Early online date	28 Oct 2024
DOIs	https://doi.org/10.1021/acs.orglett.4c03591
Publication status	E-pub ahead of print - 28 Oct 2024

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10.1021/acs.orglett.4c03591

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https://pubs.acs.org/doi/10.1021/acs.orglett.4c03591Licence: Creative Commons: Attribution (CC-BY)

1 Finished
1 Active

Boron: Beyond the Reagent
Lloyd-Jones, G.
Engineering and Physical Sciences Research Council
1/05/23 → 30/04/28
Project: Research
Transborylation: A Novel Catalysis Paradigm
Thomas, S.
Royal Society
1/12/17 → 30/09/24
Project: Research

Cite this

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title = "Hidden Boron Catalysis: A Cautionary Tale on TMEDA Inhibition",

abstract = "Hidden boron catalysis plagues catalyzed hydroboration reactions, with the “catalyst” acting to mediate the decomposition of HBpin/HBcat to BH3 which is the actual (hidden) catalyst. N,N,N′,N′-Tetramethylethylenediamine (TMEDA) has been used to identify hidden boron catalysis through trapping/inhibition. Kinetic analyses showed that TMEDA inhibition is only applicable below 60 °C and that other amine traps are likewise ineffective. Awareness of this temperature limitation reveals widespread hidden catalysis in previous methods and should limit future false negative tests.",

author = "Julie Macleod and Bage, {Andrew D.} and Meyer, {Leonie M.} and Thomas, {Stephen P.}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

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doi = "10.1021/acs.orglett.4c03591",

language = "English",

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journal = "Organic letters",

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T2 - A Cautionary Tale on TMEDA Inhibition

AU - Macleod, Julie

AU - Bage, Andrew D.

AU - Meyer, Leonie M.

AU - Thomas, Stephen P.

PY - 2024/10/28

Y1 - 2024/10/28

N2 - Hidden boron catalysis plagues catalyzed hydroboration reactions, with the “catalyst” acting to mediate the decomposition of HBpin/HBcat to BH3 which is the actual (hidden) catalyst. N,N,N′,N′-Tetramethylethylenediamine (TMEDA) has been used to identify hidden boron catalysis through trapping/inhibition. Kinetic analyses showed that TMEDA inhibition is only applicable below 60 °C and that other amine traps are likewise ineffective. Awareness of this temperature limitation reveals widespread hidden catalysis in previous methods and should limit future false negative tests.

AB - Hidden boron catalysis plagues catalyzed hydroboration reactions, with the “catalyst” acting to mediate the decomposition of HBpin/HBcat to BH3 which is the actual (hidden) catalyst. N,N,N′,N′-Tetramethylethylenediamine (TMEDA) has been used to identify hidden boron catalysis through trapping/inhibition. Kinetic analyses showed that TMEDA inhibition is only applicable below 60 °C and that other amine traps are likewise ineffective. Awareness of this temperature limitation reveals widespread hidden catalysis in previous methods and should limit future false negative tests.

U2 - 10.1021/acs.orglett.4c03591

DO - 10.1021/acs.orglett.4c03591

M3 - Article

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AN - SCOPUS:85207540028

SN - 1523-7060

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SP - 9564

EP - 9567

JO - Organic letters

JF - Organic letters

IS - 44

ER -

Hidden Boron Catalysis: A Cautionary Tale on TMEDA Inhibition

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Projects

Boron: Beyond the Reagent

Transborylation: A Novel Catalysis Paradigm

Cite this