Visible-Light-Triggered Selective Intermolecular [2+2] Cycloaddition of Extended Enones: 2-Oxo-3-enoates and 2,4-Dien-1-ones with Olefins

Lei Min Zhao, Tao Lei, Rong Zhen Liao, Hongyan Xiao, Bin Chen, Vaidhyanathan Ramamurthy, Chen Ho Tung, Li Zhu Wu

Research output: Contribution to journalArticle

Abstract

Photosensitization has recently re-emerged owing to the current interest in visible-light catalysis. One of the photoreactions investigated in this context, namely, photo[2+2]cycloaddition of olefins, is established to show high selectivity and wide generality. Here, we describe the results of our studies on selective intermolecular cycloaddition between extended enones (2,4-dien-1-ones and 2-oxo-3-enoates) and olefins under visible-light sensitization. With Ru(bpy)3Cl2 as the triplet energy sensitizer, [2+2] addition of 2,4-dien-1-ones to olefins resulted in the addition to the "ene" part of enones with high efficiency. Generality and functional group tolerance were established by examining a number of enones. 2-Oxo-3-enoates also underwent addition to olefins in the presence of Ru(phen)3(PF6)2. Both additions were more efficient in the presence of the triplet sensitizer than upon direct irradiation. No Paternò-Büchi product was detected. Density functional theory calculations revealed the origin of high selectivity in the two extended enone systems. Together with spectroscopic studies and control experiments, the cycloaddition has been demonstrated to occur from the excited triplet state of these extended enones, which were generated via the energy transfer process.

Original languageEnglish (US)
Pages (from-to)9257-9269
Number of pages13
JournalJournal of Organic Chemistry
Volume84
Issue number14
DOIs
StatePublished - Jun 18 2019
Externally publishedYes

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Cycloaddition
Alkenes
Excited states
Energy transfer
Functional groups
Catalysis
Density functional theory
Irradiation
Experiments

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Visible-Light-Triggered Selective Intermolecular [2+2] Cycloaddition of Extended Enones : 2-Oxo-3-enoates and 2,4-Dien-1-ones with Olefins. / Zhao, Lei Min; Lei, Tao; Liao, Rong Zhen; Xiao, Hongyan; Chen, Bin; Ramamurthy, Vaidhyanathan; Tung, Chen Ho; Wu, Li Zhu.

In: Journal of Organic Chemistry, Vol. 84, No. 14, 18.06.2019, p. 9257-9269.

Research output: Contribution to journalArticle

Zhao, Lei Min ; Lei, Tao ; Liao, Rong Zhen ; Xiao, Hongyan ; Chen, Bin ; Ramamurthy, Vaidhyanathan ; Tung, Chen Ho ; Wu, Li Zhu. / Visible-Light-Triggered Selective Intermolecular [2+2] Cycloaddition of Extended Enones : 2-Oxo-3-enoates and 2,4-Dien-1-ones with Olefins. In: Journal of Organic Chemistry. 2019 ; Vol. 84, No. 14. pp. 9257-9269.
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abstract = "Photosensitization has recently re-emerged owing to the current interest in visible-light catalysis. One of the photoreactions investigated in this context, namely, photo[2+2]cycloaddition of olefins, is established to show high selectivity and wide generality. Here, we describe the results of our studies on selective intermolecular cycloaddition between extended enones (2,4-dien-1-ones and 2-oxo-3-enoates) and olefins under visible-light sensitization. With Ru(bpy)3Cl2 as the triplet energy sensitizer, [2+2] addition of 2,4-dien-1-ones to olefins resulted in the addition to the {"}ene{"} part of enones with high efficiency. Generality and functional group tolerance were established by examining a number of enones. 2-Oxo-3-enoates also underwent addition to olefins in the presence of Ru(phen)3(PF6)2. Both additions were more efficient in the presence of the triplet sensitizer than upon direct irradiation. No Patern{\`o}-B{\"u}chi product was detected. Density functional theory calculations revealed the origin of high selectivity in the two extended enone systems. Together with spectroscopic studies and control experiments, the cycloaddition has been demonstrated to occur from the excited triplet state of these extended enones, which were generated via the energy transfer process.",
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