Carboazidation of Terminal Alkenes with Trimethylsilyl Azide and Cyclic Ethers Catalyzed by Copper Powder under Oxidative Conditions.

Copper-catalyzed carboazidation of alkenes with trimethylsilyl azide and cyclic ethers has been achieved. The employment of naturally abundant copper catalysts allowed cyclic ethers to be used as alkylating reagents under oxidative conditions. The use of styrene derivatives and 1,1-diaryl alkenes afforded carboazidation products. In addition, application of five- and six-membered cyclic ethers to the present reaction gave target organic molecules bearing azide and cyclic ether groups with perfect regioselectivity. Radical trapping and clock experiments revealed that the present reaction proceeded via the radical pathway. To further demonstrate the utility of this carboazidation reaction, transformations from the azide group to the related nitrogen-containing compounds were also performed.

Nickel-Catalyzed Decarbonylative Reductive Alkylation of Aroyl Fluorides with Alkyl Bromides.

This paper describes the nickel-catalyzed reductive alkylation of aroyl fluorides with alkyl bromides in a decarbonylative manner. In this reaction, various functional groups are well tolerated and the C(sp2)-C(sp3) bond can be constructed directly without the use of organometallic reagents. The present reaction is a cross-electrophile coupling via the radical pathway, affording the corresponding alkylarenes in moderate to good yields.

Transmetalation of boronic acids and their derivatives: mechanistic elucidation and relevance to catalysis.

The Suzuki-Miyaura reaction (the cross-coupling reaction of boronic acids with organic halides catalysed by Pd complexes) has been recognised as a useful synthetic organic reaction that forms a C(sp2)-C(sp2) bond. The catalytic cycle of the reaction involves the transmetalation of aryl- and alkenylboronic acids with Pd(II) complexes. It migrates the aryl and alkenyl groups of boronic acid to Pd and produces a Pd-C bond. Many studies have investigated the mechanism of transmetalation. They elucidated the mechanism of the organometallic reaction and its role as a fundamental step in catalytic reactions. This perspective reviews studies on the transmetalation of aryl- and alkenylboronic acids with Pd(II) complexes. Emphasis was laid on the structures and chemical properties of the intermediate Pd complexes and the effects of OH- on the pathways of the catalytic Suzuki-Miyaura reaction. The reactions of arylboronic acids with Rh(I)-OH complexes were investigated, which are relevant to the mechanism of Rh-catalysed addition of aryl boronic acids to enones and aldehydes. Recent studies on the transmetalation of boronic acids with other late transition metals such as Fe(II), Co(I), Pt(II), Au(III), and Au(I) are presented with the related catalytic reactions and their utilisation in the synthesis of aromatic molecules and π-conjugated materials.

Palladium/Copper-Cocatalyzed Arylsilylation of Internal Alkynes with Acyl Fluorides and Silylboranes: Synthesis of Tetrasubstituted Alkenylsilanes by Three-Component Coupling Reaction.

In this Letter, the palladium/copper-cocatalyzed arylsilylation of internal alkynes with acyl fluorides and silylboranes is described. This is the first example in which acyl fluorides have been utilized for the three-component coupling reaction via decarbonylation, yielding a variety of tetrasubstituted alkenylsilanes in moderate to good yields.

Iron-catalysed radical cyclization to synthesize germanium-substituted indolo[2,1-a]isoquinolin-6(5H)-ones and indolin-2-ones.

A simple and efficient strategy for iron-catalysed cascade radical cyclization was developed, by which an array of germanium-substituted indolo[2,1-a]isoquinolin-6(5H)-ones and indolin-2-ones were obtained in one pot with germanium hydrides as radical precursors. A rapid intramolecular radical trapping mode enabled the selective arylgermylation of alkenes over the prevalent hydrogermylation reaction.

Recent Advances in Transition-metal-catalyzed C-C Bond Formation via C(sp2 )-F Bond Cleavage.

The activation of a carbon-fluorine bond is one of the most challenging topics in modern synthetic organic chemistry due to their low reactivity compared to other carbon-halogen bonds. In this review, we present the recent developments since 2015 on cross-coupling reactions that form C-C bonds via cleavage of C(sp2 )-F bonds. Not only the conventional activation of C(sp2 )-F bonds, but also decarbonylative or carbonyl-retentive cleavage of C(acyl)-F bonds will be introduced. This paper mainly describes new protocols for the formation of C(sp2 )-C(sp3 ), C(sp2 )-C(sp2 ), and C(sp2 )-C(sp) bonds via transition-metal-catalyzed cleavage of C(sp2 )-F bonds.

Palladium-catalyzed decarbonylative and decarboxylative cross-coupling of acyl chlorides with potassium perfluorobenzoates affording unsymmetrical biaryls.

This paper describes the synthesis of unsymmetrical biaryls by the palladium-catalyzed cross-coupling reaction of acyl chlorides with potassium perfluorobenzoates. This transformation is unique in that it involves simultaneous decarbonylation and decarboxylation under redox-neutral conditions. Compared to conventional cross-coupling protocols for the synthesis of unsymmetrical biaryls, the two reactants in this synthetic strategy can be readily prepared from abundant and inexpensive aromatic carboxylic acids.

Synthesis and reactivity of boryloxorhodium complexes. Relevance to intermolecular transmetalation from boron to rhodium in Rh-catalyzed reactions.

The synthesis of a dimeric boryloxorhodium complex having the Rh-O-Bpin scaffold from the reaction of [(cod)Rh(OMe)]2 or [(cod)Rh(OH)]2 with an arylboronate has been achieved. The obtained dirhodium complex is converted into mononuclear complex [(cod)Rh(OBpin)(PPh3)], which reacts with arylboronic acid to afford the complex with an Rh-aryl bond via transmetalation from boron to rhodium. The dimeric boryloxorhodium complex catalyzes the 1,4-addition of arylboronic acid to cyclohexene-2-one.

Synthesis of Oxygen-Containing Heterocyclic Compounds by Iron-Catalyzed Alkylative Cyclization of Unsaturated Carboxylic Acids and Alcohols.

Iron-catalyzed alkylative cyclization of alkenes bearing oxygen nucleophiles with secondary and tertiary alkyl bromides through carbon-carbon and carbon-oxygen bond formations has been developed. A broad substrate scope is an attractive feature of this synthetic method, providing a variety of potentially bioactive five- and six-membered oxygen-containing heterocycles. The reaction pathway is proposed to involve a radical addition of the in situ-formed alkyl radical to an alkene followed by carbon-oxygen bond-forming intramolecular cyclization.

Synthesis of 2-Isoxazoline N-Oxides by Copper-Mediated Radical Annulation of Alkenes with α-Nitrobenzyl Bromides.

Copper-mediated [3 + 2] annulation of alkenes with α-nitrobenzyl bromides has been developed. The reaction is promoted simply by a copper salt to produce the corresponding 2-isoxazoline N-oxides with perfect regioselectivity. The present method can be conducted under mild conditions, affording a diverse array of 2-isoxazoline N-oxides. The obtained products can readily be converted to the related heterocycles such as 2-isoxazoline and isoxazole. A radical-polar crossover pathway initiated by single-electron transfer from nitronate to a copper salt is proposed.

Decarboxylative Cross-Coupling of Acyl Fluorides with Potassium Perfluorobenzoates.

We report the transition metal-free decarboxylative cross-coupling reactions of acyl fluorides with potassium perfluorobenzoates. Compared with traditional transition metal-catalyzed cross-couplings, this protocol presents an extremely environmentally benign pathway to afford unsymmetrical diaryl ketones. To install perfluorophenyl groups, this method highlights highly selective, inexpensive, and nontoxic conditions. The reaction system tolerates various functional groups in acyl fluorides. Remarkably, all of the starting materials can be prepared from abundant carboxylic acids and the reaction proceeds without any catalysts and additives.

Synthesis and Physicochemical Properties of 2,7-Disubstituted Phenanthro[2,1-b:7,8-b']dithiophenes.

We report the design, synthesis, and physicochemical properties of an array of phenanthro[2,1-b:7,8-b']dithiophene (PDT-2) derivatives by introducing five types of alkyl (CnH2n+1; n = 8, 10, 12, 13, and 14) or two types of decylthienyl groups at 2,7-positions of the PDT-2 core. Systematic investigation revealed that the alkyl length and the type of side chains have a great effect on the physicochemical properties. For alkylated PDT-2, the solubility was gradually decreased as the chain length was increased. For instance, C8-PDT-2 exhibited the highest solubility (5.0 g/L) in chloroform. Additionally, substitution with 5-decylthienyl groups showed poor solubility in both chloroform and toluene, whereas PDT-2 with 4-decylthienyl groups resulted in higher solubility. Furthermore, UV-vis absorption of PDT-2 derivatives substituted by decylthienyl groups showed a redshift, indicating the extension of their π-conjugation length. This work reveals that modification of the conjugated core by alkyl or decylthienyl side chains may be an efficient strategy by which to change the physicochemical properties, which might lead to the development of high-performance organic semiconductors.

Syntheses of polynorbornadienes by ring-opening metathesis polymerizations of symmetric and non-symmetric 2,3-bis(alkoxycarbonyl)norbornadienes and their conversion to half-ester derivatives.

Libraries of polynorbornadienes were synthesized with good yields with a ruthenium-containing 2nd generation Grubbs catalyst by ring-opening metathesis polymerization (ROMP) of a variety of symmetric and non-symmetric 2,3-bis(alkoxycarbonyl)norbornadiene monomer units prepared from the half-esters obtained efficiently by the selective monohydrolysis reactions of symmetric diesters we reported earlier. Among these polymers, the polynorbornadienes with t-butoxycarbonyl groups derived from non-symmetric monomer units were converted to the half-ester derivatives by deprotection with trifluoroacetic acid, yielding amphiphilic polymers. The hydrogenation reactions of the obtained polymers were carried out to yield polymers having saturated structures in the main chains for improvement of the thermal stabilities. All these polymers were characterized by their molecular weights and thermal properties along with the spectroscopic data. Our selective monohydrolysis reactions have been proven to be a versatile tool for production of relatively homogeneous polymer libraries.

Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes: synthesis of unsymmetrical diarylethynes.

Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes is described. This reaction not only effectively inhibits the formation of undesired homocoupled products by avoiding the addition of a base, but also exhibits a wide substrate scope to provide a general access to diverse unsymmetrical diarylethynes.

Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions.

Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp2)-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.

Synthesis of Dinaphtho[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (DNADT) Derivatives: Effect of Alkyl Chains on Transistor Properties.

To investigate organic field-effect transistor (OFET) properties, a new thienoacene-type molecule, 4,14-dihexyldinaphtho[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (C6-DNADT), consisting of π-conjugated nine aromatic rings and two hexyl chains along the longitudinal molecular axis has been successfully synthesized by sequential reactions, including Negishi coupling, epoxidation, and cycloaromatization. The fabricated OFET using thin films of C6-DNADT exhibited p-channel FET properties with field-effect mobilities (µ) of up to 2.6 × 10-2 cm2 V-1 s-1, which is ca. three times lower than that of the parent DNADT molecule (8.5 × 10-2 cm2 V-1 s-1). Although this result implies that the installation of relatively short alkyl chains into the DNADT core is not suitable for transistor application, the origins for the FET performance obtained in this work is fully discussed, based on theoretical calculations and solid-state structure of C6-DNADT by grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) analyses. The results obtained in this study disclose the effect of alkyl chains introduced onto the molecule on transistor characteristics.

Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides.

Palladium-catalyzed decarbonylative alkylation reactions of acyl fluorides have been developed using alkylboranes having ß-hydrogens. A wide range of functional groups were well tolerated, even at the high temperature required for decarbonylation. This protocol provides a diverse C(sp2)-C(sp3) bond formation via a highly efficient decarbonylative process. The hemilabile bidentate ligand DPPE plays a crucial role for retardation of the undesired ß-hydride elimination.

Nickel or Palladium-Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives.

Carboxylic acid derivatives containing acyl halides, anhydrides, esters, amides and acyl nitriles are highly appealing electrophiles in transition-metal-catalyzed carbon-carbon bond-forming reactions due to their ready availability and low cost, which can provide divergent transformations of carboxylic acids into other value-added products. In this Minireview, we focus on the recent advances of decarbonylative transformations of carboxylic acid derivatives in carbon-carbon bond formations using Ni or Pd catalysts. A series of reaction types, product classifications and reaction pathways are presented herein, which show the advantageous features of carboxylic acid derivatives as alternative to aryl or alkyl halides in terms of reactivity and compatibility. The well-accepted mechanism of nickel- or palladium-catalyzed decarbonylative transformations involves initial oxidative addition of carboxylic acid derivatives, followed by decarbonylation or transmetalation (or insertion), and reductive elimination to generate the products, thereby regenerating the catalysts.

Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling.

Copper-catalyzed regioselective aminothiolation of terminal and internal alkenes with N-fluorobenzenesulfonimide and thiols has been developed. The three-component reaction is promoted by the addition of dimethyl sulfide. In addition to aromatic alkenes, aliphatic alkenes are subjected to the reaction, affording various aminothiolation adducts as single regioisomers. The radical process is proposed by preliminary mechanistic studies, involving radical trap and radical clock experiments.

Nickel/copper-cocatalyzed decarbonylative silylation of acyl fluorides.

Ni/Cu-cocatalyzed decarbonylative silylation of acyl fluorides with silylboranes has been developed to afford various arylsilanes with high efficiency and good functional-group compatibility via carbon-fluorine bond cleavage and carbon-silicon bond formation. Such transformation can not only extend the functionalization type of acyl fluorides but complement the synthetic route for arylsilanes.