Journal ArticleDOI
Recent advances in carbon–carbon bond-forming reactions involving homoenolates generated by NHC catalysis
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TLDR
The versatility of NHC-bound homoenolate is illustrated by its annulation with various carbonyl compounds leading to gamma-butyrolactones, spiro-gamma- butyrolactsones, and delta-lactones.Abstract:
Homoenolate, a species containing anionic carbon β to a carbonyl group or a moiety that can be transformed into a carbonyl group, is a potential three carbon synthon. Recent introduction of a protocol for the generation of homoenolate directly from enals by NHC (nucleophilic heterocyclic carbene) catalysis has made it possible to explore the synthetic utility of this unique reactive intermediate. The versatility of NHC-bound homoenolate is illustrated by its annulation with various carbonyl compounds leading to γ-butyrolactones, spiro-γ-butyrolactones, and δ-lactones. Interception of homoenolate with imines afforded γ-lactams and bicyclic β-lactams. Formation of cyclopentenes and spirocyclopentanones respectively by reaction with enones and dienones is also noteworthy. This tutorial review focuses on these and other types of reactions which attest to the synthetic potential of NHC-bound homoenolates in organic synthesis.read more
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Organocatalytic umpolung: N-heterocyclic carbenes and beyond
TL;DR: This tutorial review aims at offering a didactic overview of organocatalytic umpolung and should serve as an inspiration for further progress in this field.
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The Measure of All Rings—N‐Heterocyclic Carbenes
Thomas Dröge,Frank Glorius +1 more
TL;DR: Physicochemical data (electronics, sterics, bond strength) of NHCs that are essential for the design, application, and mechanistic understanding of N-Heterocyclic carbenes in catalysis are provided.
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N-heterocyclic carbene catalyzed domino reactions.
André Grossmann,Dieter Enders +1 more
TL;DR: A critical consideration of domino, cascade, and tandem catalysis in the case of N-heterocyclic carbenes catalysts is presented and recent publications in this area are highlighted.
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Organocatalytic Asymmetric Assembly Reactions: Synthesis of Spirooxindoles via Organocascade Strategies
TL;DR: This review focuses on the enantioselective synthesis of spirooxindoles via organocascade strategies and is organized on the basis of three primary starting materials and then further subdivided according to the types of organocatalyst.
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Extending NHC-Catalysis: Coupling Aldehydes with Unconventional Reaction Partners
TL;DR: An efficient intermolecular Stetter reaction is developed for the formation of α-amino acid derivatives, with broad aldehyde scope and high enantiomeric excess, and tailor-made thiazolylidene catalysts allowed the unprecedented use of nonactivated olefins and alkynes as aldehydes coupling partners.
References
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Organocatalysis by N-Heterocyclic Carbenes
TL;DR: The inversion of the classical reactivity (Umpolung) opens up new synthetic pathways in biochemical processes as nucleophilic acylations and in nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical process as nucleophile acylation.
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Asymmetric enamine catalysis.
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Methods of Reactivity Umpolung
TL;DR: There are six principal methods of umpolung: 1 2n-oxidation, heteroatom exchange and modification, homologation and its reversal, the cyclopropane “trick”, use of acetylenes, and redox reactions; under certain circumstances none of these techniques is necessary in cases where direct umpoline is possible.