Enantioselective Synthesis of Functionalized Arenes by Nickel‐Catalyzed Site‐Selective Hydroarylation of 1,3‐Dienes with Aryl Boronates

A catalytic method for the site‐selective and enantioselective synthesis of functionalized arenes by the intermolecular hydroarylation of terminal and internal 1,3‐dienes with aryl pinacolato boronates is reported. The reactions are promoted by 5.0 mol % of a readily available monodentate phosphoramidite‐Ni complex in ethanol, affording a variety of enantioenriched products in up to 96 % yield and 99:1 er. Mechanistic studies indicate that Ni–allyl formation is irreversible and related to the nature of the arylboronate.     

Enantio- and Regioselective NiH-Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

A highly enantio- and regioselective hydroarylation process of vinylarenes with aryl halides has been developed using a NiH catalyst and a new chiral bis imidazoline ligand. A broad range of structurally diverse, enantioenriched 1,1-diarylalkanes, a structure found in a number of biologically active molecules, have been obtained with excellent yields and enantioselectivities under extremely mild conditions.     

Ni-Catalyzed Regioselective Hydroarylation of 1-Aryl-1,3-Butadienes with Aryl Halides

An efficient nickel-catalyzed regioselective hydroarylation of 1,3-dienes with aryl halides and a silane has been developed, affording a range of allylic arenes in good to excellent yields under mild conditions. This method exhibits broad substrate scope, and excellent functional group tolerance. Late-stage modification of complex architectures was demonstrated.     

Copper-Catalyzed Defluorinative Hydroarylation of Alkenes with Polyfluoroarenes

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.     

Manganese-Catalyzed Hydroarylation of Unactivated Alkenes

Transition-metal-catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8-aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese-catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese-catalysis regime. The method features earth-abundant manganese catalysis, easily available substrates, broad functional-group tolerance, and excellent regioselective control.     

Ligand-Enabled Nickel-Catalyzed Redox-Relay Migratory Hydroarylation of Alkenes with Arylborons

A redox-relay migratory hydroarylation of isomeric mixtures of olefins with arylboronic acids catalyzed by nickel complexes bearing diamine ligands is described. A range of structurally diverse 1,1-diarylalkanes, including those containing a 1,1-diarylated quaternary carbon, were obtained in excellent yields and with high regioselectivity. Preliminary experimental evidence supports the proposed non-dissociated chainwalking of aryl-nickel(II)-hydride species along the alkyl chain of alkenes before selective reductive elimination at a benzylic position. A catalyst loading as low as 0.5 mol % proved to be sufficient in large-scale synthesis while retaining high reactivity, highlighting the practical value of this transformation.     

Nickel-Catalyzed Cross-Electrophile 1,2-Silyl-Arylation of 1,3-Dienes with Chlorosilanes and Aryl Bromides

Catalytic, three-component, cross-electrophile reactions have recently emerged as a promising tool for molecular diversification, but studies have focused mainly on the alkyl-carbonations of alkenes. Herein, the scope of this method has been extended to conjugated dienes and silicon chemistry through silylative difunctionalization of 1,3-dienes with chlorosilanes and aryl bromides. The reaction proceeds under mild conditions to afford 1,2-linear-silylated products, a selectivity that is different to those obtained from conventional methods via an intermediary of H(C)-η³-π-allylmetal species. Preliminary mechanistic studies reveal that chlorosilane reacts with 1,3-diene first and then couples with aryl bromide.     

Nickel-Catalyzed Thiolation of Aryl Nitriles

A nickel-catalyzed thiolation of aryl nitriles has been developed to access functionalized aryl thioethers. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) as well as the base KO^tBu (potassium tert-butoxide) are essential to achieve this transformation. This scalable and practical process involves both a C−C bond activation and a C−S bond formation. Furthermore, this reaction shows a high functional-group tolerance and enables the late-stage functionalization of important molecules.     

Nickel-Catalyzed Electrochemical Synthesis of (Hetero)Aryl Trifluoromethyl Selenides

A convenient and efficient approach for the construction of aryl trifluoromethyl selenoethers from aryl iodides under mild conditions is reported. Electrochemical activation of stable and inexpensive NiBr₂bipy (bipy – bipyridine) complex instead of labile Ni(COD)₂ (COD – cyclooctadiene) catalyst. [NMe₄][SeCF₃] is employed as shelf-stable source of SeCF₃ fragment. The reaction tolerates a wide range of substrates, including modification of drug-like molecules. Cyclic voltammetry studies allow insight into the reaction mechanism.     

Manganese‐Catalyzed Hydroarylation of Unactivated Alkenes

Transition‐metal‐catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8‐aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese‐catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ‐ and γ‐arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese‐catalysis regime. The method features earth‐abundant manganese catalysis, easily available substrates, broad functional‐group tolerance, and excellent regioselective control.     

Rhodium‐Catalyzed Enantioposition‐Selective Hydroarylation of Divinylphosphine Oxides with Aryl Boroxines

The rhodium‐catalyzed hydroarylation of divinylphosphine oxides (RP(O)(CH=CH₂)₂) with aryl boroxines ((ArBO)₃) gives the corresponding monoarylation products (RP(O)(CH=CHAr)CH₂CH₃) in high yields. One of the two vinyl groups in the phosphine oxide undergoes oxidative arylation while the other one is reduced to an ethyl moiety. These reactions proceed with high selectivity in terms of the enantiotopic vinyl groups in the presence of (R)‐DTBM‐segphos/Rh to give the P‐stereogenic monoarylation products with high enantioselectivity.     

Enantioselective Addition of Boronates to Acyl Imines Catalyzed by Chiral Biphenols

On the big screen : A chiral biphenol catalyst screening protocol was developed for the rapid identification of enantioselective nucleophilic boronate reactions with acyl imines (see scheme). The approach successfully identified a unique catalyst for the reaction of aryl, vinyl, and alkynyl boronates. Mechanistic studies demonstrate boronate ligand exchange with the catalyst is necessary for activation towards nucleophilic addition.

     

Stereoselective Synthesis of Functionalized 1,3-Dienes in Water

An efficient synthesis of functionalized 1,3‐dienes via one‐pot reactions between dialkyl acetylenedicarboxylates?, 1,3‐dicarbonyl compounds and secondary amines in ?water as the solvent is described. The mild reaction condition high yields and the ?new products are advantages of our method.     

Enantioselective Nickel-Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes

Metal-catalyzed chain-walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chain-walking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel-catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain-walking process is demonstrated. The reaction exhibits excellent regio- and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium-labeling experiments support the chain-walking process, which involves an iterative β-H elimination and reinsertion processes. Gram-scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation.     

Synthesis of 4-Substituted-1,2-Dihydroquinolines by Means of Gold-Catalyzed Intramolecular Hydroarylation Reaction of N-Ethoxycarbonyl-N-Propargylanilines

An alternative Au(I)-catalyzed synthetic route to functionalized 1,2-dihydroquinolines is reported. This novel approach is based on the use of N-ethoxycarbonyl protected-N-propargylanilines as building blocks that rapidly undergo the IMHA reaction affording the 6-endo cyclization product in good to high yields. In the presence of N-ethoxycarbonyl-N-propargyl-meta-substituted anilines, the regiodivergent cyclization at the ortho-/para-position is achieved by the means of catalyst fine tuning.     

Hydroarylation of Styrenes with Electron-Rich Arenes Over Acidic Ion-Exchange Resins

A series of acidic cation-exchange resins were used for the hydroarylation of resorcinol with styrene, in which resin D072 exhibited the excellent catalytic performance in this reaction with 99% conversion of styrene and 90% selectivity of 4-(1-phenylethyl)resorcinol. It was applied to the hydroarylation of various electron-rich arenes with styrenes, and the hydroarylated products were quantitatively obtained. This catalyst could be used for four consecutive runs with slight decrease in activity. The hydroarylation of resorcinol with styrene over resin D072 in a fixed bed was completed effectively with 94% selectivity and 99% conversion, and this green continuous process is potentially applicable to large-scale productions.     

Nickel(0)‐Catalyzed Hydroarylation of Styrenes and 1,3‐Dienes with Organoboron Compounds

A Ni‐catalyzed hydroarylation of styrenes and 1,3‐dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes and allylarenes under redox‐neutral conditions. In this hydroarylation reaction, a new strategy that uses the proton of methanol to generate the active catalyst species Ni?H was developed. The Ni‐catalyzed hydroarylation, combined with a Ir‐catalyzed C?H borylation, affords a very efficient and straightforward access to a retinoic acid receptor agonist.