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Synfacts 2025; 21(01): 54
DOI: 10.1055/a-2467-4638
Metals in Synthesis

A New Class of Pyridine-Derived NHCs Enables Copper-Catalyzed Asymmetric Allylic Alkylation

Contributor(s):
Mark Lautens 
,
Colton E. Johnson
Bouëtard D, Zhang Z, Vives T, Cordier M, Cavallo L *, Jarrige L, Falivene L *, Mauduit M *. KAUST, Thuwal, Saudi Arabia; Università di Salerno, Fisciano, Italy; University of Rennes, France
Chiral N-Hydroxyalkyl Pyrid-2-ylidenes: A New Class of Ligands for Copper-Catalyzed Asymmetric Allylic Alkylation.

ACS Catal. 2024;
14: 16785-16794
DOI: 10.1021/acscatal.4c05243
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Keywords

copper catalysis - asymmetric allylic alkylation - N-heterocyclic carbenes - ligand design

Significance

Cavallo, Falivene, Mauduit and co-workers report a new class of pyridine-derived N-heterocyclic carbenes (NHCs) and their application towards asymmetric allylic alkylation (AAA). This ligand class enables expedient syntheses of valuable skipped diene compounds which are commonly found in natural products.


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Comment

Interestingly ligand L does not form the aminocarbene directly upon deprotonation. Following initial deprotonation with KHMDS, the resulting alkoxide rapidly forms an oxazolidine via an intramolecular cyclization. This compound rapidly ring opens in the presence of copper, leading to the active catalyst species.


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Publication History

Article published online:
20 December 2024

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