Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH4SCN : Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition
Reaction of benzyl and ethyl allenoates with TMSX (X = I, Br, Cl) and with NH4SCN were investigated in MeCN, DMF, and in imidazolium ionic liquids [BMIM][NTf2] and [BMIM][PF6] as solvent, in the presence and absence of Selectfluor. Comparative product analysis studies demonstrate that the ability of Selectflour to promote oxidative/electrophilic dihalogenation/dithiocyanation with TMSX/NH4SCN (as observed previously for 1-arylallenes) is diminished in allenoates, most significantly in reactions with TMSCl, and essentially disappearing in reactions with NH4SCN, in favor of nucleophilic/conjugate addition. The study underscores the contrasting reactivity patterns in 1-arylallenes and allenoates toward electrophilic and nucleophilic additions in halofunctionalization with TMSX/Selectfluor and thiocyanation reactions with NH4SCN/Selectfluor. These competing pathways are influenced by the nature of the anion, allene structure, and the choice of solvent.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2015 |
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| Erschienen: |
2015 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:11 |
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| Enthalten in: |
Beilstein journal of organic chemistry - 11(2015) vom: 01., Seite 1641-8 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Reddy, A Srinivas [VerfasserIn] |
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| Links: |
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| Themen: |
Allene esters |
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| Anmerkungen: |
Date Completed 15.12.2015 Date Revised 30.09.2020 published: Electronic-eCollection Citation Status PubMed-not-MEDLINE |
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| doi: |
10.3762/bjoc.11.180 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM255532075 |
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| 100 | 1 | |a Reddy, A Srinivas |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH4SCN |b Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition |
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| 500 | |a Date Completed 15.12.2015 | ||
| 500 | |a Date Revised 30.09.2020 | ||
| 500 | |a published: Electronic-eCollection | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Reaction of benzyl and ethyl allenoates with TMSX (X = I, Br, Cl) and with NH4SCN were investigated in MeCN, DMF, and in imidazolium ionic liquids [BMIM][NTf2] and [BMIM][PF6] as solvent, in the presence and absence of Selectfluor. Comparative product analysis studies demonstrate that the ability of Selectflour to promote oxidative/electrophilic dihalogenation/dithiocyanation with TMSX/NH4SCN (as observed previously for 1-arylallenes) is diminished in allenoates, most significantly in reactions with TMSCl, and essentially disappearing in reactions with NH4SCN, in favor of nucleophilic/conjugate addition. The study underscores the contrasting reactivity patterns in 1-arylallenes and allenoates toward electrophilic and nucleophilic additions in halofunctionalization with TMSX/Selectfluor and thiocyanation reactions with NH4SCN/Selectfluor. These competing pathways are influenced by the nature of the anion, allene structure, and the choice of solvent | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Selectfluor | |
| 650 | 4 | |a TMSX and NH4SCN | |
| 650 | 4 | |a allene esters | |
| 650 | 4 | |a oxidative electrophilic dihalogenation/conjugate addition | |
| 700 | 1 | |a Laali, Kenneth K |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.3762/bjoc.11.180 |3 Volltext |
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