Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2012 Jun 13;53(24):3073-3076.
doi: 10.1016/j.tetlet.2012.04.021. Epub 2012 Apr 14.

Visible light photocatalysis of intramolecular radical cation Diels-Alder cycloadditions

Shishi Lin  1 , Christian E Padilla, Michael A Ischay, Tehshik P Yoon
Affiliations

Visible light photocatalysis of intramolecular radical cation Diels-Alder cycloadditions

Shishi Lin et al. Tetrahedron Lett. .

Abstract

Intramolecular radical cation Diels-Alder reactions can be conducted under photocatalytic conditions using visible light irradiation. The photocatalyst system involves the use of a Ru(bpy)(3) (2+) chromophore and methyl viologen as a co-oxidant. These reactions enable the cycloaddition of substrates whose thermal Diels-Alder cycloadditions are electronically mismatched and thus require forcing conditions. Nevertheless, the radical cation cycloadditions can be conducted on gram scale using ambient sunlight as the only source of irradiation.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Thermal cycloaddition of electronically mismatched Diels–Alder substrate 1.
Scheme 2
Scheme 2
Comparison of photocatalyst systems for radical cation IMDA.
Scheme 3
Scheme 3
Large-scale photoreaction in ambient sunlight.
See this image and copyright information in PMC

References

    1. Roush WR. In: Comprehensive Organic Synthesis. Trost BM, Fleming I, Paquette LA, editors. Vol. 5. Pergamon Press; Oxford, U.K: 1991. pp. 513–550.
    2. Fallis AG. Acc Chem Res. 1999;32:464–474.
    3. Bear BR, Sparks SM, Shea KJ. Angew Chem Int Ed. 2001;40:820–849. - PubMed
    4. Takao KI, Munakata R, Tadano KI. Chem Rev. 2005;105:4779–4807. - PubMed
    5. Juhl M, Tanner D. Chem Soc Rev. 2009;38:2983–2992. - PubMed
    1. Wassermann A. J Chem Soc. 1942:618–621.
    2. Yates P, Eaton P. J Am Chem Soc. 1960;82:4436–4437.

    1. For reviews of radical cation Diels–Alder cycloaddition chemistry, see: Bauld NL, Bellville DJ, Harirchian B, Lorenz KT, Pabon RA, Reynolds DW, Wirth DD, Chiou HS, Marsh BK. Acc Chem Res. 1987;20:371–378.Bauld NL. Tetrahedron. 1989;45:5307–5363.

    1. Bauld NL, Bellville DJ, Pabon R, Chelsky R, Green G. J Am Chem Soc. 1983;105:2378–2382.
    2. Bellville DJ, Bauld NL, Pabon R, Gardner SA. J Am Chem Soc. 1983;105:3584–3588.
    3. Pabon RA, Bauld NL. J Am Chem Soc. 1984;106:1145–1146.
    4. Bellville DJ, Wirth DW, Bauld NL. J Am Chem Soc. 1981;103:718–720.
    5. Yueh W, Bauld NL. J Phys Org Chem. 1996;9:529–538.
    1. Maroulis AJ, Arnold DR. J Chem Soc, Chem Commun. 1979:351–352.
    2. Jones CR, Allman BJ, Mooring A, Spahic B. J Am Chem Soc. 1983;105:652–654.
    3. Pabon RA, Bellville DJ, Bauld NL. J Am Chem Soc. 1983;105:5158–5159.
    4. Calhoun GC, Schuster GB. J Am Chem Soc. 1984;106:6870–6871.
    5. Mlcoch J, Steckhan E. Angew Chem Int Ed Eng. 1985;24:412–414.
    6. Gieseler A, Steckhan E, Wiest O. Synlett. 1990:275–277.
    7. Gieseler A, Steckhan E, Wiest O, Knoch F. J Org Chem. 1991;56:1405–1411.

LinkOut - more resources