A Systems Approach to a One‐Pot Electrochemical Wittig Olefination Avoiding the Use of Chemical Reductant or Sacrificial Electrode
| dc.contributor.author | Chakraborty, Biswarup | |
| dc.contributor.author | Kostenko, Arseni | |
| dc.contributor.author | Menezes, Prashanth W. | |
| dc.contributor.author | Driess, Matthias | |
| dc.date.accessioned | 2020-11-11T08:57:39Z | |
| dc.date.available | 2020-11-11T08:57:39Z | |
| dc.date.issued | 2020-08-13 | |
| dc.date.updated | 2020-11-09T11:12:41Z | |
| dc.description.abstract | An unprecedented one‐pot fully electrochemically driven Wittig olefination reaction system without employing a chemical reductant or sacrificial electrode material to regenerate triphenylphosphine (TPP) from triphenylphosphine oxide (TPPO) and base‐free in situ formation of Wittig ylides, is reported. Starting from TPPO, the initial step of the phosphoryl P=O bond activation proceeds through alkylation with RX (R=Me, Et; X=OSO2CF3 (OTf)), affording the corresponding [Ph3POR]+X− salts which undergo efficient electroreduction to TPP in the presence of a substoichiometric amount of the Sc(OTf)3 Lewis acid on a Ag‐electrode. Subsequent alkylation of TPP affords Ph3PR+ which enables a facile and efficient electrochemical in situ formation of the corresponding Wittig ylide under base‐free condition and their direct use for the olefination of various carbonyl compounds. The mechanism and, in particular, the intriguing role of Sc3+ as mediator in the TPPO electroreduction been uncovered by density functional theory calculations. | en |
| dc.description.sponsorship | DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat" | en |
| dc.description.sponsorship | TU Berlin, Open-Access-Mittel – 2020 | en |
| dc.identifier.eissn | 1521-3765 | |
| dc.identifier.issn | 0947-6539 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/11895 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-10786 | |
| dc.language.iso | en | en |
| dc.rights | This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. | |
| dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.subject.other | bond activation | en |
| dc.subject.other | electrosynthesis | en |
| dc.subject.other | Lewis acid | en |
| dc.subject.other | phosphine oxide reduction | en |
| dc.subject.other | scandium complexes | en |
| dc.title | A Systems Approach to a One‐Pot Electrochemical Wittig Olefination Avoiding the Use of Chemical Reductant or Sacrificial Electrode | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1002/chem.202001654 | en |
| dcterms.bibliographicCitation.issue | 51 | en |
| dcterms.bibliographicCitation.journaltitle | Chemistry – A European Journal | en |
| dcterms.bibliographicCitation.originalpublishername | Wiley | en |
| dcterms.bibliographicCitation.originalpublisherplace | New York, NY | en |
| dcterms.bibliographicCitation.pageend | 11834 | en |
| dcterms.bibliographicCitation.pagestart | 11829 | en |
| dcterms.bibliographicCitation.volume | 26 | en |
| tub.accessrights.dnb | free | en |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Metallorganische Chemie und Anorganische Materialien | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.group | FG Metallorganische Chemie und Anorganische Materialien | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin | en |