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. 2013 May 3;3(5):895-902.
doi: 10.1021/cs400088e.

Visible Light Photocatalysis: The Development of Photocatalytic Radical Ion Cycloadditions

Tehshik P Yoon  1
Affiliations

Visible Light Photocatalysis: The Development of Photocatalytic Radical Ion Cycloadditions

Tehshik P Yoon. ACS Catal. .

Abstract

Photochemistry has the potential to significantly impact multiple aspects of chemical synthesis, in part because photoinduced reactions can be used to construct molecular architectures that would otherwise be difficult to produce. Nevertheless, organic chemists have been slow to embrace photochemical synthesis because of technical complications associated with the use of ultraviolet light. Our laboratory has been part of an effort to design synthetically useful reactions that utilize visible light. This strategy enables the synthesis of a diverse range of organic structures by generation of a variety of reactive intermediates under exceptionally mild conditions. This Perspective article describes the reasoning that led to the conception of our first experiments in this area, the features of our reaction design that have been most powerful in the discovery of new processes, and a few of the possible future areas in which visible light photocatalysis might have a large impact.

Keywords: Cycloadditions; Natural Products; Photocatalysis; Photochemistry; Radical ions.

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Figures

Figure 1
Figure 1
Representative structures of natural products prepared by photochemical synthesis.
Figure 2
Figure 2
Photochemical properties of Ru(bpy)32+ in MeCN.
Scheme 1
Scheme 1
Mechanism of intramolecular radical anion [2+2] cycloaddition reaction.
Scheme 2
Scheme 2
Slow photocatalytic erosion of the diastereomeric purity of [2+2] cycloadducts.
Scheme 3
Scheme 3
Representative photocatalytic radical anion cycloadditions.
Scheme 4
Scheme 4
Photocatalytic reductive coupling of enones.
Scheme 5
Scheme 5
Photocatalytic radical cation [2+2] cycloadditions of electron-rich alkenes.
Scheme 6
Scheme 6
Representative photocatalytic radical cation cycloadditions.
Scheme 7
Scheme 7
Heitziamide A does not arise from a thermal Diels–Alder cycloaddition.
Scheme 8
Scheme 8
Synthesis of heitziamide A enabled by a radical cation Diels–Alder cycloaddition.
Scheme 9
Scheme 9
Plausible biosynthetic origin of heitziamide A and B via one-electron oxidation of fagaramide.
See this image and copyright information in PMC

References

    1. Ciamician G, Silber P. Chem Ber. 1908;41:1928–1935.
    1. Esser P, Pohlmann B, Scharf HD. Angew Chem Int Ed Engl. 1994;33:2009–2023.
    2. Albini A, Fagnoni M. Green Chem. 2004;6:1–6.
    3. Fagnoni M, Dondi D, Ravelli D, Albini A. Chem Rev. 2007;107:2725–2756. - PubMed
    4. Oelgemöller M, Jung C, Mattay J. Pure Appl Chem. 2007;79:1939–1947.
    5. Albini A, Fagnoni M. ChemSusChem. 2008;1:63–66. - PubMed
    6. Protti S, Fagnoni M. Photochem Photobiol Sci. 2009;8:1499–1516. - PubMed
    7. Yoon TP, Ischay MA, Du J. Nature Chem. 2010;2:527–532. - PubMed
    1. Ciamician G. Science. 1912;36:385–394. - PubMed
    1. Zurflüh R, Dunham LL, Spain VL, Siddall JB. J Am Chem Soc. 1970;92:425–427. - PubMed
    2. Meyers A1, Fleming SA. J Am Chem Soc. 1986;108:306–307.
    1. Corey EJ, Mitra RB, Uda H. J Am Chem Soc. 1963;85:362–363.
    2. Corey EJ, Mitra RB, Uda H. J Am Chem Soc. 1964;86:485–492.