Domino Reactions of Tertiary Enamides in Organic Synthesis

Studies in recent decade have shown that tertiary enamides, once thought of as unreactive and marginally useful enamine variants, are shelf-stable yet versatile nucleophilic intermediates in organic synthesis. Many compounds, especially N-heterocycles, have been synthesized by monofunctionalization reactions of tertiary enamides. By taking advantage of intramolecular and intermolecular interception of the putative acyliminium intermediates formed by the initial nucleophilic reactions of tertiary enamides, we have established several novel difunctionalization reaction methods for constructing diverse complex fused heterocyclic products. In this Account, we summarize our endeavors to develop difunctionalization reactions of tertiary enamides in a domino fashion.1 Introduction2 Strategic Considerations3 Domino Reactions of Tertiary Enamides3.1 Type I Domino Reactions3.2 Type II Domino Reactions3.3 Type III Domino Reactions4 Conclusion and Perspectives

Recent Developments in the Asymmetric Detrifluoroacetylative Reactions of in situ Generated Mono-Fluorinated Enolates

The development of an efficient and mild synthetic methodology for the construction of bioactive fluorine-containing molecules represents one of the hot research topics in general synthetic organic chemistry. In this review, some recent progresses achieved in the development of detrifluoroacetylatively generated mono-fluorinated enolates via CC bond cleavage and their asymmetric nucleophilic reactions for assembly of chiral quaternary C-F center containing compounds.

New Organic Dyes from Phthalonitrile via Interesting Nucleophilic Reactions

Phthalonitrile (PN) is regarded mostly as an important precursor for phthalocyanine (Pc). However, the presence of two ortho triple bonds also endow PN with significant potential to form novel conjugated systems. Based on several unexpected nucleophilic reactions, our group has discovered novel applications of PN for the synthesis of asymmetric benzo-fused aza-BOIDPYs and new fused-ring phthalorubines (Pr). This Synpacts highlights our recent advances in this field.1 Introduction2 Benzo-Fused Aza-BODIPYs3 Phthalorubines4 Conclusion

Functional models of nonheme diiron enzymes: reactivity of the μ-oxo-μ-1,2-peroxo-diiron(iii) intermediate in electrophilic and nucleophilic reactions

The ambiphilic behavior (electrophilic versus nucleophilic character) of the peroxo-diferric complex and its relative reactivity towards aldehydes and phenols have been discussed.