Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer

Roman Kleinmans, Tobias Pinkert, Subhabrata Dutta, Tiffany O. Paulisch, Hyeyun Keum, Constantin G. Daniliuc and Frank Glorius ()
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Roman Kleinmans: Westfälische Wilhelms-Universität Münster
Tobias Pinkert: Westfälische Wilhelms-Universität Münster
Subhabrata Dutta: Westfälische Wilhelms-Universität Münster
Tiffany O. Paulisch: Westfälische Wilhelms-Universität Münster
Hyeyun Keum: Westfälische Wilhelms-Universität Münster
Constantin G. Daniliuc: Westfälische Wilhelms-Universität Münster
Frank Glorius: Westfälische Wilhelms-Universität Münster

Nature, 2022, vol. 605, issue 7910, 477-482

Abstract: Abstract For more than one century, photochemical [2+2]-cycloadditions have been used by synthetic chemists to make cyclobutanes, four-membered carbon-based rings. In this reaction, typically two olefin subunits (two π-electrons per olefin) cyclize to form two new C–C σ-bonds. Although the development of photochemical [2+2]-cycloadditions has made enormous progress within the last century, research has been focused on such [2π+2π]-systems, in which two π-bonds are converted into two new σ-bonds1,2. Here we report an intermolecular [2+2]-photocycloaddition that uses bicyclo[1.1.0]butanes as 2σ-electron reactants3–7. This strain-release-driven [2π+2σ]-photocycloaddition reaction was realized by visible-light-mediated triplet energy transfer catalysis8,9. A simple, modular and diastereoselective synthesis of bicyclo[2.1.1]hexanes from heterocyclic olefin coupling partners, namely coumarins, flavones and indoles, is disclosed. Given the increasing importance of bicyclo[2.1.1]hexanes as bioisosteres—groups that convey similar biological properties to those they replace—in pharmaceutical research and considering their limited access10,11, there remains a need for new synthetic methodologies. Applying this strategy enabled us to extend the intermolecular [2+2]-photocycloadditions to σ-bonds and provides previously inaccessible structural motifs.

Date: 2022
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DOI: 10.1038/s41586-022-04636-x

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