Using Restricted Bond Rotations to Enforce Excited-State Behavior of Organic Molecules

This account highlights the role of restricted bond rotations in influencing the excited-state reactivity of organic molecules. It highlights the photochemical reactivity of various organic molecules and the design strategies that could be exploited by chemists to utilize restricted bond rotations to uncover new excited-state reactivity and to achieve selectivity.

1 Introduction.

2 NEER-Principle and Restricted Bond Rotations in the Excited State

3 [2+2]-Photocycloaddition of Enamides

4 [3+2]-Photocycloaddition vs. Paternò–Büchi Reaction of Enamides

5 Divergent Photoreactivity of Enones Dictated by Restricted Bond Rotations: Norrish–Yang reactions vs. 6π-Photocyclization

6 Divergent Photoreactivity of Imides with Alkenes: [2+2]-Photocycloaddition vs. Photoene Reaction

7 Summary and Outlook

Key words

photocycloaddition - axial chiral transfer - excited-state reactivity - photocatalysis - energy transfer catalysis

Publication History

Received: 23 January 2022

Accepted after revision: 02 March 2022

Accepted Manuscript online:
02 March 2022

Article published online:
19 May 2022

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• 1b Present address: University of Pennsylvania, PA 19104, USA
• 1c Present address: LANXESS corporation, CT 06770, USA
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