Dual Copper Photoredox C-H Alkynylation with Arylacetylenes.

In the realm of organic synthesis, direct C-H alkynylation with arylacetylenes has remained a daunting challenge due to competing annulations or alkenylation. Addressing this long-standing issue, herein we demonstrate the merging of copper and photocatalysis to achieve the elusive C-H alkynylation of benzamides using arylacetylenes or arylpropiolic acids. Unlike conventional copper-mediated C-H activations, our protocol circumvents the need for high temperatures and stoichiometric amounts of copper salts or metal/non-metal oxidants.

Rh(III)-catalyzed aldehydic and aryl C-H alkylation with cyclopropanols C-H/C-C bond activation.

Herein, we report Rh(III) catalyzed aldehydic or aryl C-H alkylation C-C bond activation of cyclopropanols, facilitating the synthesis of β-functionalized ketones. The protocol employs cyclopropanol as the alkylating agent with 2-aminobenzaldehyde or aniline derivatives to access a variety of unsymmetrical 1,4-diketones or β-aryl ketones, respectively. The practicality of these transformations is showcased through the modification of natural products, gram-scale synthesis, broad substrate scope and postfunctionalizations.

Ru(II)-Catalyzed Decarboxylative (4 + 2)-Annulation of Benzoic Acids and Benzamides with Propargyl Cyclic Carbonates.

Propargyl cyclic carbonates have emerged as versatile precursors in synthetic chemistry. However, their reactivity has so far been limited to transition metal-catalyzed substitution and cyclization reactions. Herein, we illustrate the successful employment of propargyl cyclic carbonates as coupling partners in Ru(II)-catalyzed C-H annulation of benzoic acids and benzamides.

Pyrazolidinone-Aided Ru(II)-Catalyzed Regioselective C-H Annulation with Allenes.

Regioselective annulation of allenes via C-H activation represents an elegant synthetic approach toward the construction of valuable scaffolds. Considering the importance of allenes, herein we developed an unprecedented Ru(II)-catalyzed highly regioselective redox-neutral C-H activation/(4 + 1)-annulation of 1-arylpyrazolidinones employing allenyl acetates to access pyrazolo[1,2-]indazol-1-one derivatives. Additionally, allenyl cyclic carbonates, which were never tested in C-H activation, were utilized to construct a similar class of heterocycles having a pendent alcohol functionality.

Expedient radical phosphonylations ligand to metal charge transfer on bismuth.

Bismuth, in spite of its low cost and low toxicity, has found limited application in organic synthesis. Although the photoactivity of Bi(iii) salts has been well studied, this has not been effectively exploited in photocatalysis. To date, only a single report exists for the Bi-based photocatalysis, wherein carbon centered radicals were generated using ligand to metal charge transfer (LMCT) on bismuth.

Rh(iii)-catalyzed sp/sp-C-H heteroarylations cascade C-H activation and cyclization.

The development of an efficient strategy for facile access to quinoline-based bis-heterocycles holds paramount importance in medicinal chemistry. Herein, we describe a unified approach for accessing 8-(indol-3-yl)methyl-quinolines by integrating Cp*Rh(iii)-catalyzed C(sp)-H bond activation of 8-methylquinolines followed by nucleophilic cyclization with -ethynylaniline derivatives. Remarkably, methoxybiaryl ynones under similar catalytic conditions delivered quinoline tethered spiro[5.

A highly diastereoselective one-pot Ugi/radical spirocyclization/aza-Michael addition sequence.

We hereby report a highly diastereoselective synthesis of chalcogenated azaspirotricycles a one-pot Ugi/spirocyclization/aza-Michael addition sequence. The reaction proceeds a key visible light mediated spirocyclization step under mild, metal-free and energy efficient conditions. A variety of complex sulfenylated and selenylated azaspirotricycles were obtained in good yields.

Rh(II)-Catalyzed Denitrogenative Reaction of N-Sulfonyl-1,2,3-triazoles with Quinolones and Isoquinolones.

Herein, we developed an efficient approach to access biologically relevant 2-aminoquinolines and 1-aminoisoquinolines from readily available N-sulfonyl-1,2,3-triazoles and 2-quinolones or 1-isoquinolones. This transformation involves the selective O-H insertion of these derivatives onto the in situ generated Rh-azavinyl carbenes (Rh-AVC) followed by rearrangement. The reaction proceeds smoothly under operationally simple conditions and the protocol was found to be scalable.

Access to Polysubstituted Furan Derivatives via Cascade Oxy-palladation and Hydrocarbofunctionalization of Unactivated Alkenes.

The development of an expedient strategy for the synthesis of biologically relevant multisubstituted furans is a much-desired yet challenging task. Herein, we report an efficient and versatile strategy involving two different pathways for the construction of diverse polysubstituted C3- and C2-substituted γ-furanyl carboxylic acid derivatives. The synthetic approach for C3-substituted furans involves intramolecular cascade oxy-palladation of alkyne-diols followed by the regioselective coordinative insertion of unactivated alkenes.

A visible light mediated alkyl sulfonylative cascade using Hantzsch esters SO insertion.

We hereby report a visible light mediated alkyl sulfonylative cascade cyclization of alkynyl and dialkynyl cyclohexadienones SO insertion. The protocol utilizes alkyl Hantzsch esters as the alkyl source and DABSO as the SO source with 4-CzIPN as the organophotocatalyst. A variety of dihydrochromenone derivatives were obtained in good yields under mild energy efficient conditions.

Ru(II)-Catalyzed [4 + 2]-Annulation and Arylation of 1,4-Naphthoquinones.

Naphthoquinones form the core of a variety of drugs and natural products. As a result, the conjugation of 1,4-naphthoquinones with organic building blocks would offer a facile strategy toward scaffolds of biological interest. In this regard, we hereby report a Ru(II)-catalyzed [4 + 2] annulation of 1,4-naphthoquinones with benzoic acids to afford various naphthoquinone lactones.

Pd(ii)-catalyzed β- and γ-C-(sp)-H dienylation with allenyl acetates.

Recent years have seen the emergence of transition metal catalyzed C-H activation as a powerful synthetic tool in organic chemistry. Allenes have fascinated synthetic chemists due to their unique reactivity. While directing group assisted functionalization of C(sp)-H bonds with allenes is well documented in the literature, their coupling with more challenging aliphatic C(sp)-H bonds remains elusive.

Diphenyl Ditelluride: An Unconventional Reducing Agent in the Sulfonylative Cascade of Alkynyl Cyclohexadienones.

Herein, we report a reductive hydrazo-sulfonylative difunctionalization cascade of alkynyl cyclohexadienones employing PhTeTePh as an uncommon reducing agent. Diphenyl ditelluride is a commercially available solid with a good solubility profile in most organic solvents, and this is the first report illustrating it as a reducing agent. The protocol afforded a variety of difunctionalized dihydrochromenones and dihydrobenzofuranones in good yields under relatively mild conditions.

α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C-H activation: a safe carbene precursor and a weak directing group.

Transition metal-catalyzed cross-coupling of sp C-H bonds with diazo compounds carbene migratory insertion represents an efficient strategy for the construction of C-C and C-heteroatom bonds in organic synthesis. Despite the popularity of diazo compounds as coupling partners in C-H activation, they pose serious safety and stability issues due to potential exothermic reactions linked with the release of N gas. However, compared with diazo compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used in industrial scales, and easier/safer to prepare.

Ru(II)-Catalyzed Regioselective Annulation of 2-Hydroxystyrenes with Allenyl Acetates Vinylic C-H Activation.

Herein, we disclose an unprecedented and robust Ru(II)-catalyzed non-oxidative [5+1] annulation of 2-hydroxystyrenes with allenyl acetates to access biologically relevant chromene skeletons. The heteroatom on allene plays a pivotal role in controlling the regioselectivity of migratory insertion, and the reaction proceeds through a Ru-σ-allyl pathway, which has been elusive so far in C-H activation reactions with allenes. The protocol is sustainable in nature as it proceeds at room temperature and avoids the use of any toxic metal oxidants.

Substrate-Dependent Denitrogenative Rearrangements of Rhodium Azavinyl Carbenes Involving 1,2-Aryl Migration.

Herein, we disclose substrate-dependent rearrangements of 4-substituted -sulfonyl-1,2,3-triazoles under Rh(II)-catalysis via denitrogenation. The reaction pathways included key 1,2-aryl migration the formation of intermediatory phenonium ion, which is elusive so far with Rh-azavinyl carbenes. Intriguingly, the transformations were completely dependent on the substituent present leading to different scaffolds like enaminones, pyrrol-3-ones, and azadienes.

Regioselective Dichotomy in Ru(II)-Catalyzed C-H Annulation of Aryl Pyrazolidinones with 1,3-Diynes.

Herein, we present a substrate-controlled regiodivergent strategy for the selective synthesis of C3 or C2-alkynylated indoles ruthenium-catalyzed [3 + 2]-annulation of readily available pyrazolidinones and 1,3-diynes. Remarkably, C3-alkynylated indoles were obtained in good yields when 1,4-diarylbuta-1,3-diynes were employed as the coupling partners. On the other hand, dialkyl-1,3-diynes led to the selective formation of C2-alkynylated indoles.

Dual Photoredox Cobalt Catalyzed [4+1] Annulation and C-H Alkoxylation.

Herein, we developed two distinct pyridine N-oxide directed C-H activation protocols to achieve [4+1] annulation and alkoxylation of benzamide derivatives by merging Co-catalysis with visible-light photoredox catalysis. The protocols deliver the respective products in good yields under facile conditions at room temperature. The use of an inexpensive photocatalyst coupled with molecular oxygen bypassing the need of stoichiometric oxidants forms the chief highlight of the work.

Visible-Light Mediated Arbuzov-Like Reaction with Thiophenols.

We hereby disclose, a visible light mediated addition of sulfenyl radicals to trialkyl phosphites to access functionalized phosphorothioates. The use of cheap and readily available Eosin Y as a photocatalyst under mild energy efficient conditions bypassing the use of external oxidants forms the chief highlight of the work. The protocol is scalable and mechanistic studies indicate that the reaction proceeds through an ionic-Arbuzov like pathway from phosphoranyl radicals.

A metal-free four-component sulfonylation, Giese cyclization, selenylation cascade insertion of sulfur dioxide.

We hereby report a highly regio- and diastereoselective arylsulfonylation-radical cyclization-selenylation cascade of alkynyl cyclohexadienones for the facile synthesis of highly functionalized dihydrochromenones. The protocol utilizes aryldiazonium salts as aryl partners and DABSO as a benign SO source and also as a redox mediator. Additionally, we also developed a visible light mediated protocol wherein diaryliodonium salts were used as the aryl partners at room temperature.

Rh(iii)-Catalyzed [5 + 1] annulation of 2-alkenylanilides and 2-alkenylphenols with allenyl acetates.

Herein, we report a mild and highly regioselective Rh(iii)-catalyzed non-oxidative [5 + 1] vinylic C-H annulation of 2-alkenylanilides with allenyl acetates, which has been elusive so far. The reaction proceeds vinylic C-H activation, regioselective 2,3-migratory insertion, β-oxy elimination followed by nucleophilic cyclization to get direct access to 1,2-dihydroquinoline derivatives. The strategy was also successfully extended to C-H activation of 2-alkenylphenols for constructing chromene derivatives.

Pd(II)-Catalyzed Transient Directing Group-Assisted Regioselective Diverse C4-H Functionalizations of Indoles.

The development of a rational strategy for achieving site-selective C4-H halogenation of indoles is an appealing yet challenging task. Herein, we disclose a Pd(II)-catalyzed transient directing group (TDG)-assisted methodology for realizing C4 chlorination/bromination of indoles employing glycine as the TDG and NFSI as a bystanding oxidant. The use of inexpensive and commercially available CuX as the halide source is the key highlight of this protocol.

Cobalt-catalyzed highly diastereoselective [3 + 2] carboannulation reactions: facile access to substituted indane derivatives.

Efficient oxidative [3 + 2] annulation reaction involving aryl hydrazones and heterobicyclic alkenes has been realized with inexpensive and earth-abundant cobalt salts under aerobic conditions. The reaction proceeds directing-group-assisted C-H activation and -selective migratory insertion, followed by the intramolecular nucleophilic attack of the alkylcobalt(III) species onto the imine with high -diastereoselectivity to provide complex indane derivatives. The generation of three contiguous stereogenic centers within the indanyl unit and the avoidance of the use of stoichiometric amounts of metal oxidants make this transformation more valuable and appealing.

Catalytic Insertion Reactions of α-Imino Carbenoids.

Over the past decade, α-imino carbenoids generated via transition metal (such as rhodium, nickel, copper, palladium, silver) catalyzed denitrogenative ring-opening of N-sulfonyl-1,2,3-triazoles have found an extensive account of applications in synthetic organic chemistry. Particularly, they have been widely utilized as a donor/acceptor carbene complex in a range of transformations leading to diverse nitrogen containing compounds and heterocycles. Along the same direction, 3-diazoindolin-2-imines were successfully applied as an alternative source of α-imino carbenoid precursors for the development of a number of methodologies to access diverse indole derivatives.

Rh(III)-Catalyzed Stereoselective C-C Bond Cleavage of ACPs with -Phenoxyacetamides: The Critical Role of the Nucleophilic Directing Group.

Rh(III)-catalyzed redox-neutral chemodivergent coupling of -phenoxyacetamides and alkylidenecyclopropanes (ACPs) has been documented. The reaction proceeds C-H activation, regioselective migratory insertion and stereoselective β-carbon elimination followed by β-hydride elimination, resulting in -dienylation of phenols in nonpolar solvents, whereas [3 + 2]-annulation leading to dihydrobenzofurans was realized in polar fluorinated solvents. It was observed that the nucleophilic directing group controls the elimination of β-carbon and so plays a vital role for achieving high stereoselectivities.