Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 13, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202114346
Keywords
palladium; directing group; annulation; heterocycle; alkene functionalization
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Funding
- Pfizer, Inc.
- National Institutes of Health [5R35 GM125052-05, 3R35 GM125052-04S2]
- Lindemann Trust
- English-Speaking Union
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In this study, we evaluated different ambiphilic organohalides for their participation in anti-selective carbocyclic or heterocyclic annulation with non-conjugated alkenyl amides under Pd-II/Pd-IV catalysis. By optimizing the reaction conditions, we developed protocols for the synthesis of various carbocyclic or heterocyclic compounds. We also demonstrated the reactivity of otherwise unreactive ambiphilic haloketones through Pd-II/amine co-catalysis. This method proceeds via a distinct Pd-II/Pd-IV mechanism, resulting in unique reactivity and selectivity patterns.
In this study, we systematically evaluate different ambiphilic organohalides for their ability to participate in anti-selective carbo- or heteroannulation with non-conjugated alkenyl amides under Pd-II/Pd-IV catalysis. Detailed optimization of the reaction conditions has led to protocols for synthesizing tetrahydropyridines, tetralins, pyrrolidines, and other carbo/heterocyclic cores via [n+2] (n=3-5) (hetero)annulation. Expansion of scope to otherwise unreactive ambiphilic haloketones through Pd-II/amine co-catalysis is also demonstrated. Compared to other annulation processes, this method proceeds via a distinct Pd-II/Pd-IV mechanism involving Wacker-type directed nucleopalladation. This difference results in unique reactivity and selectivity patterns, as revealed through assessment of reaction scope and competition experiments.
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