Rh2(II)-Catalyzed Selective C(sp3)-H Bond Electrophilic Amination of Aryl Azide-Tethered 1,3-Dicarbonyl Compounds.

Herein, we report the accomplishment of Rh2(II)-catalyzed intramolecular amination of aryl azide-tethered 1,3-dicarbonyls to access privileged heterocyclic scaffolds with exclusive diastereoselectivity under simple reaction conditions. This method also allows an unconventional direct α-amination at electron-deficient C(sp3)-H bonds of aryl azide-tethered 1,3-diketones to afford fused 2-azatricyclo[4.4.0.02,8]decanones and 2,2-disubstituted indolines, which are present in several biologically active alkaloids. Kinetic isotope experiments revealed that the nucleophilic addition of enol π-bonds on the transient electrophilic rhodium-nitrenoid intermediate enables C-N bond formation.

Site-selective and stereoselective transformations on p-quinols & p-quinamines.

The intermolecular transformation of simple substrates into highly functionalized scaffolds with multiple stereogenic centers is an attractive strategy in modern organic synthesis. Prochiral 2,5-cyclohexadienones, being stable and easily accessible, are privileged key building blocks for the synthesis of complex molecules and bioactive natural products. In particular, p-quinols and p-quinamines are important subclasses of cyclohexadienones, having both nucleophilic and electrophilic sites, and can undergo various intermolecular cascade annulations via formal cycloadditions and other transformations. This article highlights the recent developments of intermolecular transformations on p-quinols and p-quinamines along with plausible reaction mechanisms. We hope that this review will inspire the readers to explore the new potential applications of these unique prochiral molecules.

Mechanochemical Defluorinative Arylation of Trifluoroacetamides: An Entry to Aromatic Amides.

The amide bond is prominent in natural and synthetic organic molecules endowed with activity in various fields. Among a wide array of amide synthetic methods, substitution on a pre-existing (O)C-N moiety is an underexplored strategy for the synthesis of amides. In this work, we disclose a new protocol for the defluorinative arylation of aliphatic and aromatic trifluoroacetamides yielding aromatic amides. The mechanochemically induced reaction of either arylboronic acids, trimethoxyphenylsilanes, diaryliodonium salts, or dimethyl(phenyl)sulfonium salts with trifluoroacetamides affords substituted aromatic amides in good to excellent yields. These nickel-catalyzed reactions are enabled by C-CF3 bond activation using Dy2O3 as an additive. The current protocol provides versatile and scalable routes for accessing a wide variety of substituted aromatic amides. Moreover, the protocol described in this work overcomes the drawbacks and limitations in the previously reported methods.

Stereoselective synthesis of (Z)-1,3-bis(α,ß-unsaturated carbonyl)-isoindolines from aldehydes and phenacyl azides under metal free conditions.

Here in the present manuscript, we report our observation of an unprecedented stereoselective synthesis of 2H-isoindolin-1,3-ylidenes from 2-(formylphenyl)acrylates and phenacylazide in the presence of piperidine. Unlike in our previous findings, in which we accessed 3-keto-isoquinolines from the same starting materials under slightly modified reaction conditions, this unexpected one-pot tandem reaction allows an efficient and simple method to access a variety of highly functionalized ethyl (Z)-2-((Z)-3-(2-oxo-2-arylethylidene)-2,3-dihydro-1H-benzo[e]isoindol-1-ylidene)-acetates in very good to excellent yields (up to 91%). The present methodology is compatible with a wide variety of functional groups.

Transition-Metal Catalyzed Stereoselective Desymmetrization of Prochiral Cyclohexadienones.

The development of transition-metal catalyzed enantioselective and diastereoselective transformations has contributed many advances in the field of synthetic organic chemistry. Particularly, stereoselective desymmetrization of prochiral cyclohexadienones represents a powerful strategy for accessing highly functionalized and stereochemically enriched scaffolds, which are often found in biologically active compounds and natural products. In recent years, several research groups including our group have made a significant progress on transition-metal catalyzed stereoselective desymmetrizations of 2,5-cyclohexadienones. In this account, we will provide an overview of the recent developments in this area employing Pd, Cu, Rh, Au, Ag, Ni, Co, and Mn-catalysts.

Transition-Metal-Free One-Pot Tandem Synthesis of 3-Ketoisoquinolines from Aldehydes and Phenacyl Azides.

An efficient and transition-metal-free strategy for the synthesis of 3-keto-isoquinolines in one pot has been developed from the easily accessible 2-(formylphenyl)acrylates and phenacyl azides. Various substituted aldehydes and phenacyl azides were successfully employed in this transformation to furnish a variety 3-keto-isoquinolines in very good yields. A number of controlled experiments were conducted to postulate the reaction mechanism. Secondary functionalizations of 2-keto-isoquinolins were also performed to showcase the synthetic utility.

Correction: Magnetically recoverable Cu0/Fe3O4 catalyzed highly regioselective synthesis of 2,3,4-trisubstituted pyrroles from unactivated terminal alkynes and isocyanides.

Correction for 'Magnetically recoverable Cu0/Fe3O4 catalyzed highly regioselective synthesis of 2,3,4-trisubstituted pyrroles from unactivated terminal alkynes and isocyanides' by Dipak Kumar Tiwari et al., Chem. Commun., 2016, 52, 4675-4678.

Transition-Metal-Free Approach for the Synthesis of 4-Aryl-quinolines from Alkynes and Anilines.

An efficient and transition-metal-free approach for the synthesis of 4-arylquinolines from readily available anilines and alkynes in the presence of K2S2O8 and DMSO has been developed. A variety of alkynes and anilines having a diverse range of substitution patterns can undergo the one-pot cascade process successfully. Effectively, this method uses DMSO as one carbon source, thus providing a highly atom-economical and environmentally benign approach for the synthesis of 4-arylquinolines.

Transition-Metal-Free Quinoline Synthesis from Acetophenones and Anthranils via Sequential One-Carbon Homologation/Conjugate Addition/Annulation Cascade.

A transition-metal-free method for the construction of functionalized quinolines from readily available acetophenones and anthranils is reported. This one-pot reaction cascade involves in situ generation of α,ß-unsaturated ketones from the acetophenone via one-carbon homologation by DMSO followed by the aza-Michael addition of anthranils and subsequent annulation. DMSO acted in this reaction not only as solvent but also as one carbon source, thus providing a highly atom-economical and environmentally benign approach for the synthesis of 3-substituted quinolines.

α,ß-Functionalization of saturated ketones with anthranils via Cu-catalyzed sequential dehydrogenation/aza-Michael addition/annulation cascade reactions in one-pot.

An efficient method to access functionalized quinolines from the readily available saturated ketones and anthranils has been explored. This one-pot cascade reaction involves the in situ generation of α,ß-unsaturated ketones by the copper catalysed dehydrogenation of saturated ketones followed by the aza-Michael addition of anthranils and subsequent annulation.

Magnetically recoverable Cu(0)/Fe3O4 catalyzed highly regioselective synthesis of 2,3,4-trisubstituted pyrroles from unactivated terminal alkynes and isocyanides.

An efficient, one pot tandem nano Cu(0)/Fe3O4 catalyzed highly regioselective synthesis of 3-substituted pyrrole-2,4 dicarboxylates from unactivated terminal alkynes and isocyanides has been developed. This strategy exhibits an unprecedented double addition of isocyanides on unactivated terminal alkynes to obtain trisubstituted pyrroles in high yields. Furthermore, the catalyst was magnetically recovered and reused five times without any appreciable loss of activity.