An Expedient Radical Approach for the Decarboxylative Synthesis of Stereodefined All-Carbon Tetrasubstituted Olefins.
Angew Chem Int Ed Engl
; 63(26): e202403651, 2024 Jun 21.
Article
em En
| MEDLINE
| ID: mdl-38619179
ABSTRACT
We report a user-friendly approach for the decarboxylative formation of stereodefined and complex tri- and tetra-substituted olefins from vinyl cyclic carbonates and amines as radical precursors. The protocol relies on easy photo-initiated α-amino-radical formation followed by addition onto the double bond of the substrate resulting in a sequence involving carbonate ring-opening, double bond relay, CO2 extrusion and finally O-protonation. The developed protocol is efficient for both mismatched and matched polarity substrate combinations, and the scope of elaborate stereodefined olefins that can be forged including drug-functionalized derivatives is wide, diverse and further extendable to other types of heterocyclic and radical precursors. Mechanistic control reactions show that the decarboxylation step is a key driving force towards product formation, with the initial radical addition under steric control.
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MEDLINE
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En
Ano de publicação:
2024
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Article