Singha, T and Kadam, GA and Hari, DP (2023) Photocatalyzed Dowd-Beckwith radical-polar crossover reaction for the synthesis of medium-sized carbocyclic compounds. In: Chemical Science .
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Abstract
The Dowd-Beckwith reaction, a ring-expansion of carbonyl compounds via alkoxy radicals, is a powerful approach for synthesizing medium to large-sized carbocyclic scaffolds, which takes advantage of existing ring structures and avoids entropic and enthalpic factors that arise from the end-to-end cyclization strategies. However, the Dowd-Beckwith ring-expansion followed by H-atom abstraction is still the dominating pathway, which hampers its synthetic applications, and there currently exist no reports on the functionalization of ring-expanded radicals using non-carbon based nucleophilic reagents. Herein, we report a redox-neutral decarboxylative Dowd-Beckwith/radical-polar crossover (RPC) sequence that delivers functionalized medium-sized carbocyclic compounds with broad functional group tolerance. The reaction allows one-carbon ring-expansion of 4-, 5-, 6-, 7-, and 8-membered ring substrates and can also be applied to three-carbon chain incorporation, enabling remote functionalization in medium-sized rings.
| Item Type: | Journal Article |
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| Publication: | Chemical Science |
| Publisher: | Royal Society of Chemistry |
| Additional Information: | The copyright for this article belongs to the Author. |
| Keywords: | Carbon; Carbonyl compounds; Expansion; Scaffolds, A-RINGS; Alkoxy radicals; Cyclizations; Dowd-beckwith ring expansion; End to end; Functionalizations; Large-sized; Photocatalyzed; Ring expansion; Rings structure, Cyclization |
| Department/Centre: | Division of Chemical Sciences > Organic Chemistry |
| Date Deposited: | 18 Jul 2023 11:03 |
| Last Modified: | 18 Jul 2023 11:03 |
| URI: | https://eprints.iisc.ac.in/id/eprint/82469 |
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