Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Abstract

Tertiary enamides display versatile reactivity and great stability compared to their enamine congeners. This review covers progress made in the development of new methods involving the enaminic reactivity of tertiary enamides with respect to the synthesis of complex nitrogen-containing compounds. A focus on the preparation of biologically active molecules is also presented. The syntheses reported herein are classified based on their reaction type. In addition, mechanistic insights are given for most of the new transformations.1 Introduction2 [2+2] Cycloadditions3 [4+2] Cycloadditions4 Electrocyclizations and Cycloisomerizations5 Sigmatropic Rearrangements6 Nucleophilic Additions7 Tertiary Enamides as Electrophiles8 Cross-Coupling Reactions9 Tertiary-Enamide-Assisted Reactions10 Conclusion and Perspectives

Metal free regio – and stereoselective semireduction of CF3-substituted N-allenamides

“…Enamides and allylic amides represent bioactive pharmacophores in drug molecules and have become more popular reagents for the incorporation of nitrogen-based functional groups. 3 In particular, unsaturated nitrogen containing fluorinated compounds are of ongoing interest in synthetic methodologies. 4 Nonetheless, the semireduction of allenes is confronted with significant challenges such as the control of chemo-, regio-, and stereo-selectivities.…”

Copper-Catalyzed 1,2-Difunctionalization Trifluoromethylamidation of Alkynes Assisted by a Coordinating Group

“…The enamide is a privilege subunit in pharmaceuticals and biomolecules featuring excellent biological and physiological properties, as well as being a useful and versatile synthetic platform for further elaboration in organic synthesis . In recent years, the trifluoromethyl unit has become one of the most widely utilized groups in drug molecular discovery, and the benefit of trifluoromethyl group in medicinal chemistry has long been understood .…”

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

“…Enamides are substrates of high value in organic synthesis [ 1 – 2 ]. Their multifacial reactivity has been explored in asymmetric alkylations [ 3 ], hydroalkynylations [ 4 ], trifluoromethylcyanations [ 5 ], heterocycle synthesis [ 6 ], asymmetric acylations [ 7 ], hydroborations [ 8 ], hydrogenations [ 9 ], etc.…”