Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst

We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal‐free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non‐pairwise mechanism of H(2) transfer to alkynes that normally p...

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Autores principales: Zakharov, Danila O., Chernichenko, Konstantin, Sorochkina, Kristina, Yang, Shengjun, Telkki, Ville‐Veikko, Repo, Timo, Zhivonitko, Vladimir V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303582/
https://www.ncbi.nlm.nih.gov/pubmed/34928532
http://dx.doi.org/10.1002/chem.202103501
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author Zakharov, Danila O.
Chernichenko, Konstantin
Sorochkina, Kristina
Yang, Shengjun
Telkki, Ville‐Veikko
Repo, Timo
Zhivonitko, Vladimir V.
author_facet Zakharov, Danila O.
Chernichenko, Konstantin
Sorochkina, Kristina
Yang, Shengjun
Telkki, Ville‐Veikko
Repo, Timo
Zhivonitko, Vladimir V.
author_sort Zakharov, Danila O.
collection PubMed
description We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal‐free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non‐pairwise mechanism of H(2) transfer to alkynes that normally prevents parahydrogen‐induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT‐alkyne‐H(2) intermediates through substantial (1)H, (11)B and (15)N signal enhancement and allowed advanced characterization of the catalytic process.
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spelling pubmed-93035822022-07-28 Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst Zakharov, Danila O. Chernichenko, Konstantin Sorochkina, Kristina Yang, Shengjun Telkki, Ville‐Veikko Repo, Timo Zhivonitko, Vladimir V. Chemistry Communications We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal‐free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non‐pairwise mechanism of H(2) transfer to alkynes that normally prevents parahydrogen‐induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT‐alkyne‐H(2) intermediates through substantial (1)H, (11)B and (15)N signal enhancement and allowed advanced characterization of the catalytic process. John Wiley and Sons Inc. 2022-01-19 2022-02-07 /pmc/articles/PMC9303582/ /pubmed/34928532 http://dx.doi.org/10.1002/chem.202103501 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Zakharov, Danila O.
Chernichenko, Konstantin
Sorochkina, Kristina
Yang, Shengjun
Telkki, Ville‐Veikko
Repo, Timo
Zhivonitko, Vladimir V.
Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title_full Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title_fullStr Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title_full_unstemmed Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title_short Parahydrogen‐Induced Polarization in Hydrogenation Reactions Mediated by a Metal‐Free Catalyst
title_sort parahydrogen‐induced polarization in hydrogenation reactions mediated by a metal‐free catalyst
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303582/
https://www.ncbi.nlm.nih.gov/pubmed/34928532
http://dx.doi.org/10.1002/chem.202103501
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