Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation
Abstract Alcohols are one of the most common organic compound classes among natural and synthetic products. Thus, methods for direct removal of C−OH groups without the need for wasteful pre‐functionalization are of great synthetic interest to unlock the full synthetic potential of the compound class...
| Κύριοι συγγραφείς: | , , , , , , , , |
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| Μορφή: | Άρθρο |
| Γλώσσα: | English |
| Έκδοση: |
Wiley-VCH
2023-11-01
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| Σειρά: | ChemElectroChem |
| Θέματα: | |
| Διαθέσιμο Online: | https://doi.org/10.1002/celc.202300420 |
| _version_ | 1827752502962946048 |
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| author | Dr. Piret Villo Malin Lill Zainab Alsaman Adrian Soto Kronberg Victoria Chu Dr. Guillermo Ahumada Dr. Hemlata Agarwala Prof. Mårten Ahlquist Ass. Prof. Helena Lundberg |
| author_facet | Dr. Piret Villo Malin Lill Zainab Alsaman Adrian Soto Kronberg Victoria Chu Dr. Guillermo Ahumada Dr. Hemlata Agarwala Prof. Mårten Ahlquist Ass. Prof. Helena Lundberg |
| author_sort | Dr. Piret Villo |
| collection | DOAJ |
| description | Abstract Alcohols are one of the most common organic compound classes among natural and synthetic products. Thus, methods for direct removal of C−OH groups without the need for wasteful pre‐functionalization are of great synthetic interest to unlock the full synthetic potential of the compound class. Herein, electroreductive C−OH bond activation and subsequent deoxygenative C−H and C−C bond formation of benzylic and propargylic alcohols are demonstrated along with mechanistic insights. Experimental and theoretical studies indicate that the reductive C−OH bond cleavage furnishes an open shell intermediate that undergoes a radical‐polar crossover to the corresponding carbanion that subsequently undergoes protonation to furnish alkane products. Furthermore, we demonstrate that the carbanion can be trapped with CO2 to form arylacetic acids. The cathodic transformations are efficiently balanced by the anodic oxidation of sub‐stoichiometric borohydride additives, a strategy that serves as a highly attractive alternative to the use of sacrificial metal anodes. |
| first_indexed | 2024-03-11T07:18:15Z |
| format | Article |
| id | doaj.art-1ca3a2f6e8ae444c99787ac9f4e557dc |
| institution | Directory Open Access Journal |
| issn | 2196-0216 |
| language | English |
| last_indexed | 2024-03-11T07:18:15Z |
| publishDate | 2023-11-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemElectroChem |
| spelling | doaj.art-1ca3a2f6e8ae444c99787ac9f4e557dc2023-11-17T08:08:58ZengWiley-VCHChemElectroChem2196-02162023-11-011022n/an/a10.1002/celc.202300420Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride OxidationDr. Piret Villo0Malin Lill1Zainab Alsaman2Adrian Soto Kronberg3Victoria Chu4Dr. Guillermo Ahumada5Dr. Hemlata Agarwala6Prof. Mårten Ahlquist7Ass. Prof. Helena Lundberg8KTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenPresent address: Technical University of Munich (TUM) Campus Straubing for Biotechnology and Sustainability Uferstraße 53 94315 Straubing GermanyKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenKTH Royal Institute of Technology Department of Chemistry Teknikringen 30 SE-100 44 Stockholm SwedenAbstract Alcohols are one of the most common organic compound classes among natural and synthetic products. Thus, methods for direct removal of C−OH groups without the need for wasteful pre‐functionalization are of great synthetic interest to unlock the full synthetic potential of the compound class. Herein, electroreductive C−OH bond activation and subsequent deoxygenative C−H and C−C bond formation of benzylic and propargylic alcohols are demonstrated along with mechanistic insights. Experimental and theoretical studies indicate that the reductive C−OH bond cleavage furnishes an open shell intermediate that undergoes a radical‐polar crossover to the corresponding carbanion that subsequently undergoes protonation to furnish alkane products. Furthermore, we demonstrate that the carbanion can be trapped with CO2 to form arylacetic acids. The cathodic transformations are efficiently balanced by the anodic oxidation of sub‐stoichiometric borohydride additives, a strategy that serves as a highly attractive alternative to the use of sacrificial metal anodes.https://doi.org/10.1002/celc.202300420alcoholsborohydridecarboxylationC−OH bond cleavageelectrochemistry |
| spellingShingle | Dr. Piret Villo Malin Lill Zainab Alsaman Adrian Soto Kronberg Victoria Chu Dr. Guillermo Ahumada Dr. Hemlata Agarwala Prof. Mårten Ahlquist Ass. Prof. Helena Lundberg Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation ChemElectroChem alcohols borohydride carboxylation C−OH bond cleavage electrochemistry |
| title | Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation |
| title_full | Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation |
| title_fullStr | Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation |
| title_full_unstemmed | Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation |
| title_short | Electroreductive Deoxygenative C−H and C−C Bond Formation from Non‐Derivatized Alcohols Fueled by Anodic Borohydride Oxidation |
| title_sort | electroreductive deoxygenative c h and c c bond formation from non derivatized alcohols fueled by anodic borohydride oxidation |
| topic | alcohols borohydride carboxylation C−OH bond cleavage electrochemistry |
| url | https://doi.org/10.1002/celc.202300420 |
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