Probing the Atomic Erosion Wear Characteristics of TiC-Coated Fe in Oil and Gas Drilling Environments.

The titanium carbide (TiC) coating is considered one of the key coating materials to resist erosion wear in oil and gas drilling environments due to its excellent impact and wear resistance. Based on molecular dynamics, the erosion wear resistance of TiC coatings and the pure Fe system in the simulation of nanoindentation, scratch, and particle impact was studied at the microscale. The results indicate that TiC coatings can effectively enhance the load-bearing capacity of the Fe substrate within the critical load range and exhibit low friction characteristics and erosion resistance. However, the protection is lost after the TiC coating cracks, leading to an increase in the tangential force. In addition, when TiC coatings and pure Fe systems exhibit typical erosion characteristics of brittle materials, the TiC coating will significantly reduce the erosion wear of the substrate.

What Determines the Low-Friction Mechanism of the Silicon-Doped Diamond-like Carbon Film in a Water Environment: An Atomic-Level Understanding.

It is widely acknowledged that doping silicon can significantly enhance the friction performance of diamond-like carbon (DLC) films in a water environment. However, the mechanism of low friction caused by doped silicon is still highly controversial. Therefore, this article compares the interface interaction between DLC and Si-DLC films in a water environment through first-principles calculations of physisorption and chemisorption effects. The results indicate that water molecules are predominantly chemically adsorbed rather than physically adsorbed on the Si-DLC surface. Further study reveals that when OH-termination is formed on the Si-DLC surface, water molecules are predominantly physically adsorbed rather than chemically adsorbed on the Si-DLC hydroxylation surface. Consequently, a more stable hydration layer is formed on the surface through the hydrogen bond network formed by Si-OH groups, ultimately leading to lower friction. Moreover, molecular dynamics simulations further suggest that the lower friction coefficient of Si-DLC films in a water environment may be due to more water molecules at the friction interface and fewer interface covalent bonds. In short, the low-friction coefficient of the Si-DLC film in a water environment may be caused not only by the chemisorption of water molecules on its surface but also by the physisorption of water molecules on the Si-DLC film after surface hydroxylation.

Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization.

Axially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well-established axially chiral 6-membered biaryl skeletons, examples of 5-membered biaryls have been quite scarce, and mono-substituted 3-arylpyrrole atropisomers have not been reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X-H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation-involved cyclization and elucidate the origin of enantioselectivity.

Copper-Catalyzed Enantioselective Doyle-Kirmse Reaction of Azide-Ynamides via α-Imino Copper Carbenes.

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for the construction of C(sp3 )-S and C-C bonds. Although significant advances have been achieved, the asymmetric versions via the generation of sulfonium ylides from metal carbenes have been rarely reported to date, and they have so far been limited to diazo compounds as metal carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse reaction via azide-ynamide cyclization, leading to the practical and divergent assembly of an array of chiral [1,4]thiazino[3,2-b]indoles bearing a quaternary carbon stereocenter in generally moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle-Kirmse reaction via a non-diazo approach and an unprecedented asymmetric [2,3]-sigmatropic rearrangement via α-imino metal carbenes.

Transition Metal-Free Hydrogenolysis of Anilines to Arenes Mediated by Lithium Hydride.

Hydrodenitrogenation (HDN) of nitrogen-containing organic compounds such as aniline and its derivatives is of scientific interest and practical importance. Major efforts have been devoted to the development and understanding of transition metal-mediated chemical processes. Herein, we report a fundamentally different strategy using a transition metal-free material, that is, lithium hydride (LiH) enabling the hydrogenolysis of aniline to benzene and ammonia via a chemical looping approach. Aniline reacts with LiH to form lithium anilide, and subsequently, the hydrogenolysis of lithium anilide yields benzene and ammonia and regenerates LiH to complete the loop. This LiH-mediated chemical looping HDN process stands in sharp contrast to the transition metal-catalyzed or -mediated processes, which commonly lead to the complete hydrogenation of aromatic rings. A highly denitrogenated product formation rate of 2623 µmol·g-1·h-1 is achieved for the hydrogenolysis of lithium anilide at 300 °C and 10 bar H2, which exceeds the catalytic rate of transition metal catalysts. Computational studies reveal that the scission of C-N bonds is facilitated by a Li-mediated nucleophilic attack of hydride to the α-sp2C atom of aniline. This work not only provides a distinctive chemical looping route for HDN, but also opens up materials space for the denitrogenation of anilines.

Catalyst-Dependent Stereospecific [3,3]-Sigmatropic Rearrangement of Sulfoxide-Ynamides: Divergent Synthesis of Chiral Medium-Sized N,S-Heterocycles.

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides, enabling divergent and atom-economic synthesis of a series of valuable medium-sized N,S-heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement.

Enantioselective functionalization of unactivated C(sp3)-H bonds through copper-catalyzed diyne cyclization by kinetic resolution.

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although the chemistry of vinyl cations has been vigorously studied in C(sp3)-H functionalization reactions, the catalytic enantioselective C(sp3)-H functionalization based on vinyl cations, especially for an unactivated C(sp3)-H bond, has scarcely explored. Here, we report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp3)-H insertion reaction via a kinetic resolution, affording both chiral polycyclic pyrroles and diynes with generally excellent enantioselectivities and excellent selectivity factors (up to 750). Importantly, this reaction demonstrates a metal-catalyzed enantioselective unactivated C(sp3)-H functionalization via vinyl cation and constitutes a kinetic resolution reaction based on diyne cyclization. Theoretical calculations further support the mechanism of vinyl cation-involved C(sp3)-H insertion reaction and elucidate the origin of enantioselectivity.

Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes.

The asymmetric Büchner reaction and related arene cyclopropanations represent one type of the powerful methods for enantioselective dearomatization. However, examples of asymmetric Büchner reactions via a non-diazo approach are quite scarce, and the related arene cyclopropanation based on alkynes has not been reported. Herein, we disclose an asymmetric Büchner reaction and the related arene cyclopropanation by copper-catalyzed controllable cyclization of N-propargyl ynamides via vinyl cation intermediates, leading to chiral tricycle-fused cycloheptatrienes and benzonorcaradienes in high yields and enantioselectivities. Importantly, this protocol represents an asymmetric arene cyclopropanation reaction of alkynes and an asymmetric Büchner reaction based on vinyl cations.

Copper-catalyzed enantioselective diyne cyclization via C(sp2)-O bond cleavage.

The functionalization of etheric C-O bonds via C-O bond cleavage is an attractive strategy for the construction of C-C and C-X bonds in organic synthesis. However, these reactions mainly involve C(sp3)-O bond cleavage, and a catalyst-controlled highly enantioselective version is extremely challenging. Here, we report a copper-catalyzed asymmetric cascade cyclization via C(sp2)-O bond cleavage, allowing the divergent and atom-economic synthesis of a range of chromeno[3,4-c]pyrroles bearing a triaryl oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Importantly, this protocol not only represents the first [1,2]-Stevens-type rearrangement via C(sp2)-O bond cleavage, but also constitutes the first example of [1,2]-aryl migration reactions via vinyl cations.

Asymmetric formal C-C bond insertion into aldehydes via copper-catalyzed diyne cyclization.

The formal C-C bond insertion into aldehydes is an attractive methodology for the assembly of homologated carbonyl compounds. However, the homologation of aldehydes has been limited to diazo approach and the enantioselective reaction was rarely developed. Herein, we report an asymmetric formal C-C bond insertion into aldehydes through diyne cyclization strategy. In the presence of Cu(I)/SaBOX catalyst, this method leads to the efficient construction of versatile axially chiral naphthylpyrroles in moderate to excellent yields with good to excellent enantioselectivities. This protocol represents a rare example of asymmetric formal C-C bond insertion into aldehydes using non-diazo approach. The combined experimental and computational mechanistic studies reveal the reaction mechanism, origin of regioselectivity and stereoselectivity. Notably, the chiral phosphine ligand derived from synthesized axially chiral skeleton was proven to be applicable to asymmetric catalysis.

Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides: atroposelective synthesis of axially chiral 7-aryl indolines.

Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis of axially chiral molecules. Most of these atroposelective reactions of alkynes rely on transition-metal catalysis, and the organocatalytic approaches are largely limited to special alkynes which act as the precursors of Michael acceptors. Herein, we disclose an organocatalytic atroposelective intramolecular (4 + 2) annulation of enals with ynamides. This method allows the efficient and highly atom-economical preparation of various axially chiral 7-aryl indolines in generally moderate to good yields with good to excellent enantioselectivities. Computational studies were carried out to elucidate the origins of regioselectivity and enantioselectivity. Furthermore, a chiral phosphine ligand derived from the synthesized axially chiral 7-aryl indoline was proven to be potentially applicable to asymmetric catalysis.