Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives : An Experimental and Theoretical Study
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim..
The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2015 |
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| Erschienen: |
2015 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:21 |
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| Enthalten in: |
Chemistry (Weinheim an der Bergstrasse, Germany) - 21(2015), 50 vom: 07. Dez., Seite 18280-9 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Tejedor, David [VerfasserIn] |
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| Links: |
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| Themen: |
Domino reactions |
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| Anmerkungen: |
Date Completed 01.04.2016 Date Revised 15.12.2015 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/chem.201503171 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM254149006 |
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| 245 | 1 | 0 | |a Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives |b An Experimental and Theoretical Study |
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| 500 | |a Date Completed 01.04.2016 | ||
| 500 | |a Date Revised 15.12.2015 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | ||
| 520 | |a The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a domino reactions | |
| 650 | 4 | |a microwave chemistry | |
| 650 | 4 | |a organocatalysis | |
| 650 | 4 | |a synthetic methods | |
| 650 | 4 | |a total synthesis | |
| 700 | 1 | |a Cotos, Leandro |e verfasserin |4 aut | |
| 700 | 1 | |a Márquez-Arce, Daniel |e verfasserin |4 aut | |
| 700 | 1 | |a Odriozola-Gimeno, Mikel |e verfasserin |4 aut | |
| 700 | 1 | |a Torrent-Sucarrat, Miquel |e verfasserin |4 aut | |
| 700 | 1 | |a Cossío, Fernando P |e verfasserin |4 aut | |
| 700 | 1 | |a García-Tellado, Fernando |e verfasserin |4 aut | |
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