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A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
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Vicinal α,β-functionalizations of amines: cyclization versus dehydrogenative hydrolysis
Fan Jiang1, Mathieu Achard2, Christian Bruneau1
1UMR6226 CNRS, Institut des Sciences Chimiques de Rennes, Université de Rennes1, OMC: Organometallics: Materials and Catalysis, Campus de Beaulieu, 35042 Rennes Cedex (France).
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 20, 2015
Summary
Ruthenium or iridium catalysts enable direct difunctionalization of cyclic amines. This reaction yields alpha-alkylated lactams through a novel dehydrogenative hydrolysis process, generating hydrogen from water.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Tertiary cyclic amines are prevalent structural motifs in pharmaceuticals and natural products.
- Efficient methods for their direct functionalization are highly sought after in synthetic chemistry.
Purpose of the Study:
- To develop a novel catalytic method for the direct vicinal α,β-difunctionalization of tertiary cyclic amines.
- To explore the synthesis of α-alkylated lactams from readily available starting materials.
Main Methods:
- Utilizing ruthenium or iridium transition-metal complexes with phosphine-sulfonate chelates.
- Optimizing reaction conditions including temperature, solvent, and catalyst loading.
- Employing a range of tertiary cyclic amines as substrates.
Main Results:
- Achieved direct vicinal α,β-difunctionalization of tertiary cyclic amines.
- Synthesized α-alkylated lactams via a formal dehydrogenative hydrolysis pathway.
- Observed the generation of one molecule of hydrogen from water during the reaction.
Conclusions:
- The developed catalytic system provides a new route for amine functionalization.
- This method offers a sustainable approach to lactam synthesis by utilizing water as a hydrogen source.
- The findings expand the toolkit for constructing complex amine-containing molecules.
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