Copper-Catalyzed Chemoselective Coupling of N-Dithiophthalimides and Alkyl Halides: Synthesis of Unsymmetrical Disulfides and Sulfides.

In this paper, we report an unprecedented copper-catalyzed disulfides or sulfides coupling reaction involving unactivated alkyl halides and N-dithiophthalimides. This reaction can be conducted under mild conditions using low-cost metal catalysts and exhibits high chemical selectivity and functional group compatibility, enabling the efficient assembly of various sulfides and disulfides.

Visible Light-Catalyzed Reactions of Polysulfide (DBSPS) with Aryldiazonium.

A visible light-catalyzed radical coupling reaction of polysulfide reagents with aryldiazonium was developed, which gave thiosulfonates under mild conditions. In this reaction, the thiosulfonates were isolated in good yields with a broad tolerance to functional groups. And the synthesis of diaryl monosulfides were achieved through a step-by-step reaction of two molecular aryldiazonium with DBSPS, where the sulfur source was provided by DBSPS. It was worth noting that the reaction of this monosulfides could also be achieved by a one pot two-step process. The described polysulfide reagents were able to produce three new radicals: sulfonyl radicals, sulfur-sulfonyl radicals and sulfur-sulfur-sulfonyl radicals.

Overcoming Radical Stability Order via DABCO-Triggered Desulfurization: Visible-Light-Promoted 1,2,4-Trifunctionalization of Butenyl Benzothiazole Sulfone with Thiosulfonate.

A radical 1,2,4-trifunctional reaction of thiosulfonate to unactivated olefin is achieved by a migration strategy under mild conditions. In this reaction, the more unstable primary free radicals are in situ generated after the migration of heteroaryl groups in the presence of DABCO. This trifunctionalization of unactivated olefins involves two C-S bond formations and one C-C bond formation.

Regioselective Thiol-yne Reaction of Thiol with ((Methyl-d3)sulfonyl)ethyne: Synthesis of (2-((Methyl-d3)sulfonyl)vinyl)sulfides.

Herein, we have developed a new method for the synthesis of ((methyl-d3)sulfonyl)ethyne, which is cost-effective and environmentally friendly and can be synthesized at the gram level. As an ideal thiol-yne reagent, it can be reacted with various types of thiols to afford (Z)- and (E)-type vinyl sulfides under different conditions with high selectivity. In addition, it can complete the conformational transition from Z- to E-type products under suitable conditions, and can also carry out further derivatization smoothly. The deuterium content of all products was greater than 99%. The preliminary mechanistic studies support the visible light-mediated radical course, and herein provide a novel and efficient synthetic strategy for the direct introduction of deuterated methyl groups, enriching the methods for the construction of C-S bond-containing compounds.

Simultaneous Preparation of Sulfides/Selenides and Sulfones via Synergistic Nickel-Catalyzed Reductive Coupling and SN2 Reaction.

Sulfone compounds and thioether compounds are two highly valuable classes of compounds, but it is challenging to prepare sulfone and thioether compounds simultaneously and efficiently. Here we report that sulfides/selenides and sulfones can be obtained simultaneously using allyl bromide/benzyl bromide-activated alkyl bromides and thiosulfonates/selenosulfonates using a nickel-catalyzed reductive coupling and SN2 synergistic strategy, which is characterized by excellent atom and step economy, mild reaction conditions, broad functional group compatibility, and excellent yields.

Nickel-Catalyzed Acid Chlorides with Tetrasulfides for the Synthesis of Thioesters and Acyl Disulfides.

Herein, we report a novel method for the synthesis of thioesters and acyl disulfides via nickel-catalyzed reductive cross-electrophile coupling of acid chlorides with tetrasulfides. This approach for the synthesis of thioesters and acyl disulfides is convenient and practical under mild reaction conditions, relying on easy availability. In addition, a wide range of thioesters and acyl disulfides were obtained in medium to good yields with good functional group tolerance. Moreover, thioesters and acyl disulfides can also be prepared at the gram scale, indicating that they have certain potential for industrial application.

Clinical Efficacy and Imaging Observation of Three Surgical Approaches in Treatment of Thoracolumbar Fractures.

Objective: To observe the efficacy and imaging of surgical treatment of thoracolumbar fractures via the paravertebral muscle space approach. Methods: A retrospective analysis was conducted on patients with thoracolumbar fractures receiving surgery in Baoding First Central Hospital from January 2019 to December 2020. According to different surgical approaches, they were divided into paravertebral approach group, posterior median approach group and minimally invasive percutaneous approach group. They received surgery via the paravertebral muscle space approach, posterior median approach and minimally invasive percutaneous approach, respectively. Results: Statistically significant differences were found in surgical duration, intraoperative bleeding volume, intraoperative fluoroscopy frequency, postoperative drainage volume and hospital stay among the three groups. One year after surgery, the VAS, ADL and JOA scores of the paravertebral approach group and the minimally invasive percutaneous approach group had statistically significant differences from the posterior median approach group (P < 0.05). Conclusion: For the surgical treatment of thoracolumbar fractures, the clinical efficacy of the paravertebral muscle space approach is superior to that of the traditional posterior median approach, and the clinical efficacy of the minimally invasive percutaneous approach is similar to that of the posterior median approach. All the three approaches can effectively improve the postoperative function and pain symptoms of patients without increasing the incidence of complications. Compared with the posterior median approach, the surgery via the paravertebral muscle space and minimally invasive percutaneous approaches presents shorter surgical duration, less bleeding and shorter hospital stay, which is more conducive to postoperative recovery of patients.

Copper-Catalyzed Synthesis of S-S Bond-Containing Silanols from SCBs and Trisulfide-1,1-dioxides.

In this work, an efficient method for the copper-catalyzed ring-opening hydrolysis of silacyclobutanes to silanols was developed. This strategy has the advantages of friendly reaction conditions, simple operation, and good functional group compatibility. No additional additives are required in the reaction, and the S-S bond can also be introduced into the organosilanol compounds in one step. Furthermore, the success at the gram scale demonstrates the great potential of the developed protocol for practical industrial applications.

Synthesis of 1,3-Dibenzenesulfonylpolysulfane (DBSPS) and Its Application in the Preparation of Aryl Thiosulfonates from Boronic Acids.

Herein, we provide a novel method for the synthesis of 1,3-dibenzenesulfonylpolysulfane (DBSPS), which further reacts with boronic acids to afford thiosulfonates. Commercially available boron compounds greatly expanded the range of thiosulfonates. Experimental and theoretical mechanistic investigations suggested that DBSPS could provide both thiosulfone fragments and dithiosulfone fragments, but the generated aryl dithiosulfonates were unstable and decomposed into thiosulfonates.

Identification of the mitophagy-related diagnostic biomarkers in hepatocellular carcinoma based on machine learning algorithm and construction of prognostic model.

Background and aims: As a result of increasing numbers of studies most recently, mitophagy plays a vital function in the genesis of cancer. However, research on the predictive potential and clinical importance of mitophagy-related genes (MRGs) in hepatocellular carcinoma (HCC) is currently lacking. This study aimed to uncover and analyze the mitophagy-related diagnostic biomarkers in HCC using machine learning (ML), as well as to investigate its biological role, immune infiltration, and clinical significance. Methods: In our research, by using Least absolute shrinkage and selection operator (LASSO) regression and support vector machine- (SVM-) recursive feature elimination (RFE) algorithm, six mitophagy genes (ATG12, CSNK2B, MTERF3, TOMM20, TOMM22, and TOMM40) were identified from twenty-nine mitophagy genes, next, the algorithm of non-negative matrix factorization (NMF) was used to separate the HCC patients into cluster A and B based on the six mitophagy genes. And there was evidence from multi-analysis that cluster A and B were associated with tumor immune microenvironment (TIME), clinicopathological features, and prognosis. After then, based on the DEGs (differentially expressed genes) between cluster A and cluster B, the prognostic model (riskScore) of mitophagy was constructed, including ten mitophagy-related genes (G6PD, KIF20A, SLC1A5, TPX2, ANXA10, TRNP1, ADH4, CYP2C9, CFHR3, and SPP1). Results: This study uncovered and analyzed the mitophagy-related diagnostic biomarkers in HCC using machine learning (ML), as well as to investigate its biological role, immune infiltration, and clinical significance. Based on the mitophagy-related diagnostic biomarkers, we constructed a prognostic model(riskScore). Furthermore, we discovered that the riskScore was associated with somatic mutation, TIME, chemotherapy efficacy, TACE and immunotherapy effectiveness in HCC patients. Conclusion: Mitophagy may play an important role in the development of HCC, and further research on this issue is necessary. Furthermore, the riskScore performed well as a standalone prognostic marker in terms of accuracy and stability. It can provide some guidance for the diagnosis and treatment of HCC patients.

Photoinduced Construction of Thieno[3,4-c]quinolin-4(5H)-ones/Selenopheno[3,4-c]quinolin-4(5H)-ones Using Diphenyl Disulfide or Diphenyl Diselenide as Sulfur or Selenium Sources.

A photocatalytic synthesis of thieno[3,4-c]quinolin-4(5H)-ones/selenopheno[3,4-c]quinolin-4(5H)-ones using diphenyl disulfide or diphenyl diselenide as sulfur or selenium sources was developed. Two C-S/Se bonds and one C-C bond were constructed simultaneously without transition metals and other additives.

Cu-catalyzed efficient construction of S (Se)-containing functional organosilicon compounds.

A Cu-catalyzed cascade reaction of four-membered silacyclobutanes (SCBs) and thiosulfonates to construct S (Se)-containing organosilicon compounds was developed. The protocol shows a wide range of substrate scope, high functional group compatibility and mild reaction conditions. New C-S (Se) and Si-O bonds were constructed in one step.

Efficient preparation of unsymmetrical disulfides by nickel-catalyzed reductive coupling strategy.

Disulfides are widely found in natural products and find a wide range of applications in life sciences, materials chemistry and other fields. The preparation of disulfides mainly rely on oxidative couplings of two sulfur containing compounds. This strategy has many side reactions and other shortcomings. Herein, we describe the reductive nickel-catalyzed cross-electrophile coupling of unactivated alkyl bromides with symmetrical alkyl- and aryltetrasulfides to form alkyl-alkyl and aryl-alkyl unsymmetrical disulfides. This approach for disulfide synthesis is practical, relies on easily available, unfunctionalized substrates, and is scalable. We investigated the mechanism of this transformation and found that the tetrasulfide compound does not selectively break the central S-S bond, but regio-selectively generates trisulfide intermediates.

[Effect of spinopelvic sagittal parameters and facet joint angle on degenerative lumbar spondylolisthesis].

OBJECTIVE: To investigate the effect and correlation of spinopelvic sagittal parameters and facet joint angle on degenerative lumbar spondylolisthesis. METHODS: From July 2016 to September 2019, a total of 120 patients with L4-L5 single segment degenerative spondylolisthesis were selected as observation objects (spondylolisthesis group), and 120 patients with L4-L5 single-segment degenerative spinal stenosis matched by gender and age were selected as the control group. The following parameters were measured by imaging data:pelvic incidence (PI), pelvic tilt (PT), sacral slope (SS), lumbar lordosis (LL), thoracic kyphosis (TK), sagittal vertical axis (SVA), L4-L5 cephalic facet joint angle, caudal facet joint angle and facet asymmetry.The differences of parameters between the two groups were compared and the meaningful parameters were analyzed by Logistic regression. The correlations between facet joint direction and spinopelvic parameters in patients with degenerative lumbar spondylolisthesis were analyzed. RESULTS: There were significant differences in PI, PT, LL, SVA, cephalic facet angle and caudal facet angle between two groups (P<0.05). Logistic regression analysis showed that PI, PT and cephalic facet joint angle were the risk factors for lumbar spondylolisthesis (P<0.05). The sagittal of the cephalic facet joint in spondylolisthesis group was significantly correlated with PI and PT(P<0.05). CONCLUSION: High PI, PT and sagittal of cephalic facet joint are the risk factors for lumbar spondylolisthesis, and the sagittal degree of facet joints is closely related to high PI and PT.

Visible-Light-Triggered Sulfonylation/Aryl Migration/Desulfonylation and C-S/Se Bond Formation Reaction: 1,2,4-Trifunctionalization of Butenyl Benzothiazole Sulfone with Thiosulfonate/Selenosulfonates.

A visible-light-triggered radical cascade sulfonylation/aryl migration/desulfonylation and C-S/Se bond formation reaction of butenyl benzothiazole sulfone with thiosulfonates or selenosulfonates is developed. This study affords the 1,2,4-trifunctionalization of butenyl benzothiazole sulfone derivatives under mild conditions.

Fe-S Catalyst Generated In Situ from Fe(III)- and S3•--Promoted Aerobic Oxidation of Terminal Alkenes.

An iron-sulfur complex formed by the simple mixture of FeCl3 with S3•- generated in situ from K2S is developed and applied to selective aerobic oxidation of terminal alkenes. The reaction was carried out under an atmosphere of O2 (balloon) and could proceed on a gram scale, expanding the application of S3•- in organic synthesis. This study also encourages us to explore the application of an Fe-S catalyst in organic reactions.

Nickel-Catalyzed Reductive Thiolation of Unactivated Alkyl Bromides and Arenesulfonyl Cyanides.

The cross-electrophile coupling between unactivated alkyl bromides with arenesulfonyl cyanides catalyzed by Ni(acac)2 under reductive conditions to form unsymmetrical sulfides is developed. This approach for sulfide synthesis is practical, relies on available, unfunctionalized materials such as alkyl (pseudo)halides, and is scalable. This catalytic strategy provides a complementary method for the preparation of unsymmetrical alkyl-aryl sulfides under mild conditions with good functional group tolerance.

Transition-Metal-Free Decarboxylative Cyclization of N-Arylacrylamides with 2,2-Difluoro-2-(phenylthio)acetic Acid: Synthesis of Thiodifluorooxindole Derivatives.

An efficient transition-metal-free decarboxylative cyclization of N-arylacrylamides with 2,2-difluoro-2-(phenylthio)acetic acid for the construction of thiodifluoroindoleone derivatives is described. This strategy features stable and readily available substrates, mild reaction conditions, and transition-metal-free catalysts. Notably, this protocol has successfully applied to synthesis of gem-difluoroalkenes, which exist in numerous biologically active compounds.

Visible-Light-Promoted Cross-Coupling Reactions of Aryldiazonium Salts with S-Methyl-d3 Sulfonothioate or Se-Methyl-d3 Selenium Sulfonate: Synthesis of Trideuteromethylated Sulfides, Sulfoxides, and Selenides.

A novel visible-light-photocatalytic deuterated thiomethylation/methylselenation of aryldiazonium salts utilizing S/Se-methyl-d3 sulfonothioate has been developed. The mild conditions and the various functional groups provide a green protocol for the efficient and rapid introduction of the S-CD3 or Se-CD3 group with useful levels of deuterium content (>91% D). Trideuteromethyl sulfoxides have also been successfully chemoselectively observed by simple atmospheric changes under photocatalytic conditions.