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Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source
An efficient electrochemical method for the selective oxidation of C–H bonds of unactivated alkanes (BDE ≤97 kcal mol(−1)) and C[double bond, length as m-dash]C bonds of alkenes using a biomimetic iron complex, [(bTAML)Fe(III)-OH(2)](−), as the redox mediator in an undivided electrochemical cell wit...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162932/ https://www.ncbi.nlm.nih.gov/pubmed/34094416 http://dx.doi.org/10.1039/d0sc03616a |
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author | Chandra, Bittu K. M., Hellan Pattanayak, Santanu Gupta, Sayam Sen |
author_facet | Chandra, Bittu K. M., Hellan Pattanayak, Santanu Gupta, Sayam Sen |
author_sort | Chandra, Bittu |
collection | PubMed |
description | An efficient electrochemical method for the selective oxidation of C–H bonds of unactivated alkanes (BDE ≤97 kcal mol(−1)) and C[double bond, length as m-dash]C bonds of alkenes using a biomimetic iron complex, [(bTAML)Fe(III)-OH(2)](−), as the redox mediator in an undivided electrochemical cell with inexpensive carbon and nickel electrodes is reported. The O-atom of water remains the source of O-incorporation in the product formed after oxidation. The products formed upon oxidation of C–H bonds display very high regioselectivity (75 : 1, 3° : 2° for adamantane) and stereo-retention (RC ∼99% for cyclohexane derivatives). The substrate scope includes natural products such as cedryl acetate and ambroxide. For alkenes, epoxides were obtained as the sole product. Mechanistic studies show the involvement of a high-valent oxoiron(v) species, [(bTAML)Fe(V)(O)](−) formed via PCET (overall 2H(+)/2e(−)) from [(bTAML)Fe(III)-OH(2)](−) in CPE at 0.80 V (vs. Ag/AgNO(3)). Moreover, electrokinetic studies for the oxidation of C–H bonds indicate a second-order reaction with the C–H abstraction by oxoiron(v) being the rate-determining step. |
format | Online Article Text |
id | pubmed-8162932 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81629322021-06-04 Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source Chandra, Bittu K. M., Hellan Pattanayak, Santanu Gupta, Sayam Sen Chem Sci Chemistry An efficient electrochemical method for the selective oxidation of C–H bonds of unactivated alkanes (BDE ≤97 kcal mol(−1)) and C[double bond, length as m-dash]C bonds of alkenes using a biomimetic iron complex, [(bTAML)Fe(III)-OH(2)](−), as the redox mediator in an undivided electrochemical cell with inexpensive carbon and nickel electrodes is reported. The O-atom of water remains the source of O-incorporation in the product formed after oxidation. The products formed upon oxidation of C–H bonds display very high regioselectivity (75 : 1, 3° : 2° for adamantane) and stereo-retention (RC ∼99% for cyclohexane derivatives). The substrate scope includes natural products such as cedryl acetate and ambroxide. For alkenes, epoxides were obtained as the sole product. Mechanistic studies show the involvement of a high-valent oxoiron(v) species, [(bTAML)Fe(V)(O)](−) formed via PCET (overall 2H(+)/2e(−)) from [(bTAML)Fe(III)-OH(2)](−) in CPE at 0.80 V (vs. Ag/AgNO(3)). Moreover, electrokinetic studies for the oxidation of C–H bonds indicate a second-order reaction with the C–H abstraction by oxoiron(v) being the rate-determining step. The Royal Society of Chemistry 2020-09-24 /pmc/articles/PMC8162932/ /pubmed/34094416 http://dx.doi.org/10.1039/d0sc03616a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Chandra, Bittu K. M., Hellan Pattanayak, Santanu Gupta, Sayam Sen Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title | Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title_full | Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title_fullStr | Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title_full_unstemmed | Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title_short | Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and C[double bond, length as m-dash]C bonds using water as the oxygen source |
title_sort | oxoiron(v) mediated selective electrochemical oxygenation of unactivated c–h and c[double bond, length as m-dash]c bonds using water as the oxygen source |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162932/ https://www.ncbi.nlm.nih.gov/pubmed/34094416 http://dx.doi.org/10.1039/d0sc03616a |
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