Nazarov cyclisations initiated by DDQ-oxidised pentadienyl ether: a mechanistic investigation from the DFT perspective

Literature Information

Publication Date 2018-11-08
DOI 10.1039/C8OB02590H
Impact Factor 3.876
Authors

Ali Gouranourimi, Antony Chipman, Rasool Babaahmadi, Angus Olding, Brian F. Yates, Alireza Ariafard


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Abstract

The Nazarov cyclisation is an important and reliable reaction for the synthesis of cyclopentenones. Density functional theory (DFT) has been utilised to study the mechanism of Nazarov cyclisations initiated by oxidation of pentadienyl ethers by a benzoquinone derivative (DDQ), as recently reported by West et al. (Angew. Chem., Int. Ed., 2017, 56, 6335). We determined that the reaction is most likely initiated by a hydride transfer from the pentadienyl ether to an oxygen of DDQ through a concerted pathway and not a single electron transfer mechanism. This oxidation by hydride abstraction leads to the formation of a pentadienyl cation from which the 4π electrocyclisation occurs, giving an alkoxycyclopentenyl cation. The ensuing cation is subsequently deprotonated by the reduced DDQ to afford an enol ether product. Consistent with experimental results, the hydride transfer is calculated to be the rate determining step and it can be accelerated by using electron donating substituents on the pentadienyl ether substrate. Indeed, the electron donating substituents increase the HOMO energy of the ether, making it more reactive toward oxidation. It is predicted that an unsubstituted benzoquinone, due to having a higher lying LUMO, shows much less reactivity than DDQ. Interestingly, we found an excellent correlation between the hydride transfer activation energy and the gap between the ether HOMO and the benzoquinone LUMO. From this correlation, we propose a predictive formula for reactivity of different types of substrates in the corresponding reaction.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
CiteScore: 3.4
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Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

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