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. 2011 Jun 17;67(24):4442-4448.
doi: 10.1016/j.tet.2011.02.066.

Visible Light Photocatalysis of Radical Anion Hetero-Diels-Alder Cycloadditions

Anna E Hurtley  1 , Megan A Cismesia, Michael A Ischay, Tehshik P Yoon
Affiliations

Visible Light Photocatalysis of Radical Anion Hetero-Diels-Alder Cycloadditions

Anna E Hurtley et al. Tetrahedron. .

Abstract

We have discovered a photocatalytic intramolecular hetero-Diels-Alder reaction of tethered bis(enones). This transformation involves the intermediacy of an enone radical anion and constitutes the formal coupling of an electron-deficient heterodiene with an electronically mismatched enone dienophile. The diastereoselectivity and regioselectivity of the process are high, and the dihydropyran products are amenable to a variety of synthetically useful transformations.

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Figures

Scheme 1
Scheme 1
Photocatalytic [2+2] and [4+2] cycloadditions.
Scheme 2
Scheme 2
Proposed mechanism for regioselective hetero-Diels–Alder cycloaddition of unsymmetrical bis(enone) 6.
Scheme 3
Scheme 3
Diastereoselective functionalization of 4.
See this image and copyright information in PMC

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