Synthesis of Cycloaliphatic Polyamides via Palladium-Catalyzed Hydroaminocarbonylative Polymerization.

Polyamides represent one class of materials that is important in modern society. Because of the numerous potential applications of polyamides in various fields, there is a high demand for new polyamide structures, which necessitates the development of new polymerization methods. Herein, we report a novel and efficient palladium-catalyzed hydroaminocarbonylative polymerization of dienes and diamines for the synthesis of cycloaliphatic polyamides. The method employs readily available starting materials, proceeds in an atom-economic manner, and creates a series of new functional polyamides in high yields and high molecular weights. In contrast with the traditional polyamides based on adipic acid, the cycloaliphatic polyamides have superior thermal resistance, higher glass-transition temperature, and better solubility in common organic solvents, thus probably featuring the merits of high-performance and good processability.

Palladium-Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes.

In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, the disfavored inward isomerization-hydrocarbonylation of alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed inward isomerization-hydroaminocarbonylation of unactivated alkenes and aniline hydrochlorides for the formation of synthetically valuable α-aryl carboxylic amides in high yields and high site-selectivities. The high efficiency of the reaction is attributed to a relay catalysis strategy, in which the Markovnikov-favored [PdH]-PtBu3 catalyst is responsible for inward isomerization, while the [PdH]-Ruphos catalyst is responsible for hydroaminocarbonylation of the resulting conjugated aryl alkenes. The reaction exhibits highly functional group tolerance and provides a new method for formal carbonylation of remote C(sp3)-H bond.

Synthesis of Self-healing and Light-, Thermal-, and Humidity-induced Deformative Polyurethane Actuator.

Intelligent actuating materials have drawn enormous attention because of their potential applications in soft robots, smart sensors, bionics, etc. Aiming to integrate light, thermal, and humidity stimuli deformations and self-healing function into a single polymer, a smart actuating polyurethane material CPPU-50 is designed and successfully synthesized through co-polymerization of azobenzene-containing Azo-C12 , polyethylene glycol 200 (PEG200), and 4,4'-diphenylmethane diisocyanate (MDI) at a ratio of 1:1:2. The obtained polyurethane CPPU-50 exhibits good photoinduced bending, thermal responsive shape memory effect, humidity triggered deflections and self-healing properties. Furthermore, an actuator combining light and thermal stimuli is created and the self-healing CPPU-50 film can withstand the object of 1800 times without tearing. This work can pave a way for further development of long-lived multi-stimuli-responsive actuating devices and intelligent materials.

Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon.

Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.

Palladium-Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2-Arylpropanoic Acids.

Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for the synthesis of carboxylic acids. Herein, we reported the development of a palladium-catalyzed highly enantioselective Markovnikov hydroxycarbonylation of vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in the reaction. The reaction tolerates a range of functional groups, and provides a facile and atom-economical approach to an array of 2-arylpropanoic acids including several commonly used non-steroidal anti-inflammatory drugs. The catalytic system has also enabled an asymmetric Markovnikov hydroalkoxycarbonylation of vinyl arenes with alcohols to afford 2-arylpropanates. Mechanistic investigations suggested that the hydropalladation is irreversible and is the regio- and enantiodetermining step, while hydrolysis/alcoholysis is probably the rate-limiting step.

Palladium-Catalyzed Enantioselective Heck Carbonylation with a Monodentate Phosphoramidite Ligand: Asymmetric Synthesis of (+)-Physostigmine, (+)-Physovenine, and (+)-Folicanthine.

Reported herein is the development of the first enantioselective monodentate ligand assisted Pd-catalyzed domino Heck carbonylation reaction with CO. The highly enantioselective domino Heck carbonylation of N-aryl acrylamides and various nucleophiles, including arylboronic acids, anilines, and alcohols, in the presence of CO was achieved. A novel monodentate phosphoramidite ligand, Xida-Phos, has been developed for this reaction and it displays excellent reactivity and enantioselectivity. The reaction employs readily available starting materials, tolerates a wide range of functional groups, and provides straightforward access to a diverse array of enantioenriched oxindoles having ß-carbonyl-substituted all-carbon quaternary stereocenters, thus providing a facile and complementary method for the asymmetric synthesis of bioactive hexahydropyrroloindole and its dimeric alkaloids.

A copper-catalyzed reaction of oximes with diisopropyl azodicarboxylate: an alternative method for the synthesis of oxime carbonates.

A new Cu-catalyzed efficient protocol is described for the transformation of oximes to the corresponding carbonate derivatives. Diisopropyl azodicarboxylate acted as a selective new precursor for the synthesis of oxime carbonates in high yields. The O-H bond cleavage and O-C bond formation occur in the presence of a copper catalyst providing a synthetically useful process, which tolerates a wide range of functional groups.

Friedel-Crafts Fluoroacetylation of Indoles with Fluorinated Acetic Acids for the Synthesis of Fluoromethyl Indol-3-yl Ketones under Catalyst- and Additive-Free Conditions.

A simple and efficient protocol for the fluoroacetylation of indoles is reported. The reaction uses fluorinated acetic acids as the fluoroacetylation reagents to synthesize diverse fluoromethyl indol-3-yl ketones in good yields under catalyst- and additive-free conditions. In addition, the only byproduct is water in this transformation. The synthetic utility of this reaction was also demonstrated by the concise synthesis of α-(trifluoromethyl)(indol-3-yl)methanol and indole-3-carboxylic acid.

Palladium-catalyzed oxidative carbonylation of aromatic C-H bonds of N-alkylanilines with CO and alcohols for the synthesis of o-aminobenzoates.

A Pd(II)-catalyzed C-H monocarbonylation of N-alkylanilines for the synthesis of o-aminobenzoates has been developed. Various aliphatic alcohols and phenol were tolerated in the reaction to afford the corresponding o-aminobenzoates in good yields under mild balloon pressure of CO.

[Preparation and stability of ß-carotene loaded using mesoporous silica nanoparticles as carriers system].

1,3,5-Trimethylbenzene (1,3,5-TMB) was used as the pore-enlarging modifier to expand the pore size of MCM-41 (mobil company of matter) mesoporous silica nanoparticles. The solvent impregnation method was adopted to assemble non-water-soluble ß-carotene into the pore channel of MCM-41. The MCM-41 and drug assemblies were characterized by TEM, FT-IR, elemental analysis and N2 adsorption-desorption. The results showed that MCM-41 has good sphericity and regular pore structure. The research also investigated the optimal loading time, the drug loading and the vitro stability of the ß-carotene. As a drug carrier, the modified MCM-41 showing a shorter drug loading time, the drug loading as high as 85.58% and the stability of ß-carotene in drug assemblies has improved. The study of this new formulation provides a new way for ß-carotene application.

Copper-promoted oxidative coupling of enamides and alkynes for the synthesis of substituted pyrroles.

An efficient copper-promoted oxidative coupling of enamides with alkynes has been developed for the synthesis of substituted pyrroles. The reaction proceeded through C-H and N-H bond functionalization of enamides under mild conditions.

Palladium-catalyzed carbonylation of o-iodoanilines for synthesis of isatoic anhydrides.

A novel palladium-catalyzed oxidative double carbonylation of o-iodoanilines for the synthesis of isatoic anhydrides has been developed. The reaction employs readily available o-iodoanilines as the starting materials and proceeds under mild conditions. For extension, palladium-catalyzed oxidative carbonylation of anthranilic acids was developed for the synthesis of substituted isatoic anhydrides in high to excellent yields.

Copper-catalyzed direct synthesis of iodoenamides from ketoximes.

Iodide in copper's pathway: A new, efficient, and practical copper-catalyzed synthesis of Z-iodoenamides from readily available ketoximes has been developed (see scheme). The reaction was believed to proceed through a single-electron-transfer pathway. The corresponding Z-iodoenamides have been applied to the synthesis of substituted oxazoles, dienes, ß-phenoxyl enamides, eneynes, ß-acylenamides, and pyrroles (DCE = 1,2-dichloroethane).

Enantioselective Palladium-Catalyzed Domino Carbonylative Heck Esterification of o-Iodoalkenylbenzenes with Arylboronic Acids.

The current investigation presents an innovative palladium-catalyzed asymmetric carbonylative Heck esterification method. This approach facilitates the efficient synthesis of various chiral γ-ketoacid esters by utilizing o-alkenyliodobenzenes and arylboronic acids as primary substrates. This reaction achieves the creation of three carbon-carbon bonds, two carbon-oxygen bonds, and the establishment of a quaternary carbon center within a single step. The α-chiral γ-ketoacid esters were obtained in yields ranging from good to high yields, displaying enantiomeric excesses (ee's) levels up to 92% under mild reaction conditions.

Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides.

Novel strategy for acid chlorides formation that do not use carboxylic acids is particularly attractive in chemical synthesis but remains challenging. Herein, we reported the development of a highly effective Pd-catalyzed hydrochlorocarbonylation of alkenes with CO for the formation of alkyl acid chlorides. Chlorosilane and AcOH were found as a mild HCl source for the reaction. The reaction shows broad substrate scope and produces both branched and linear alkyl acid chlorides in good to high yields upon different ligands and solvents. Cooperating with follow-up acylation reactions, the Pd-catalyzed hydrochlorocarbonylation offers a complementary platform for the synthesis of diverse carbonyl compounds from alkenes. Mechanistic investigations suggested that the reaction proceeded though a palladium hydride pathway, and CO prompted reductive elimination of the acyl-Pd-Cl intermediate.

C(alkyl)-C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction.

Activation and cleavage of carbon-carbon (C-C) bonds is a fundamental transformation in organic chemistry while inert C-C bonds cleavage remains a long-standing challenge. Retro-Diels-Alder (retro-DA) reaction is a well-known and important tool for C-C bonds cleavage but less been explored in methodology by contrast to other strategies. Herein, we report a selective C(alkyl)-C(vinyl) bond cleavage strategy realized through the transient directing group mediated retro-Diels-Alder reaction of a six-membered palladacycle, which is obtained from an in situ generated hydrazone and palladium hydride species. This unprecedented strategy exhibits good tolerances and thus offers new opportunities for late-stage modifications of complex molecules. DFT calculations revealed that an intriguing retro-Pd(IV)-Diels-Alder process is possibly involved in the catalytic cycle, thus bridging both Retro-Diels-Alder reaction and C-C bond cleavage. We anticipate that this strategy should prove instrumental for potential applications to achieve the modification of functional organic skeletons in synthetic chemistry and other fields involving in molecular editing.

Gate-tunable transport in van der Waals topological insulator Bi4Br4nanobelts.

Bi4Br4is a quasi-one-dimensional van der Waals topological insulator with novel electronic properties. Several efforts have been devoted to the understanding of its bulk form, yet it remains a challenge to explore the transport properties in low-dimensional structures due to the difficulty of device fabrication. Here we report for the first time a gate-tunable transport in exfoliated Bi4Br4nanobelts. Notable two-frequency Shubnikov-de Haas oscillations oscillations are discovered at low temperatures, with the low- and high-frequency parts coming from the three-dimensional bulk state and the two-dimensional surface state, respectively. In addition, ambipolar field effect is realized with a longitudinal resistance peak and a sign reverse in the Hall coefficient. Our successful measurements of quantum oscillations and realization of gate-tunable transport lay a foundation for further investigation of novel topological properties and room-temperature quantum spin Hall states in Bi4Br4.

Palladium-catalyzed regioselective carbonylation of C-H bonds of N-alkyl anilines for synthesis of isatoic anhydrides.

A Pd-catalyzed regioselective C-H bond carbonylation of N-alkyl anilines for the synthesis of isatoic anhydrides has been developed. The key Pd-catalyst intermediate has been isolated and characterized. This novel Pd-catalyzed carbonylation reaction tolerates a wide range of functional groups and is a reliable method for the rapid elaboration of readily available N-alkyl anilines into a variety of substituted isatoic anhydrides under mild conditions.

Synthesis of enamides via CuI-catalyzed reductive acylation of ketoximes with NaHSO3.

CuI-catalyzed reductive acylation of ketoximes for preparation of enamides was reported. A broad scope of enamides was obtained in high yields with NaHSO(3) used as the terminal reductant.

Rhodium-Catalyzed Enantioselective and Desymmetrizative Pauson-Khand Reaction: Access to Tricyclo[6.2.1.04,11]undecenes.

Rhodium-catalyzed asymmetric desymmetrization Pauson-Khand reaction of C4-alkynyl-tethered cyclohexadienones has been developed as a novel strategy for access to fused 6-5-5 tricycles bearing three consecutive stereogenic centers. An array of chiral tricyclo[6.2.1.04,11]undecenes have been synthesized in high yields and enantioselectivities in a single step under mild conditions. This strategy employs readily accessible internal-olefin-containing 1,6-enynes, providing a potentially powerful tool for constructing chiral polycyclic scaffolds of complex molecules containing cyclopentenones and cyclohexenones.