LiBr-Catalyzed C3-Disulfuration between Indole and N-Dithiophthalimide.

A simple, green halide-catalyzed protocol for disulfuration of indole derivatives with N-dithiophthalimides has been developed. This C-H disulfide reaction proceeded smoothly at room temperature with economical LiBr as catalyst, providing an effective method for the synthesis of novel unsymmetrical disulfides. A series of 3-dithioindole derivatives were obtained in high yields with good functional group tolerance; moreover, the wide scope of Harpp reagents (aryl, benzyl, primary, secondary, tertiary) confirmed the practicability of this approach.

Lewis-Acid-Catalyzed Selective Friedel-Crafts Reaction or Annulation between Anilines and Glyoxylates.

A Lewis-acid-catalyzed selective reaction between anilines and glyoxylates was developed for synthesis of diarylmethanes or oxoimidazolidines. Under the catalysis of AgOTf, a series of anilines-based diarylmethanes, including primary, secondary, and tertiary anilines, were obtained in moderate to good yields. Moreover, stereoselective oxoimidazolidines were performed with the catalysis of Cu(OAc)2·H2O.

An Electrochemical Way to Generate Amphiphiles from Hydrazones for the Synthesis of 1,2,4-Triazole Scaffold Cyclic Compounds.

An electro-oxidative cyclization pathway in which hydrazones are selected as starting materials to generate amphiphiles by reacting with benzylamines and benzamides was reported. This strategy successfully prepared a series of 1,2,4-triazoles in satisfactory yields. Moreover, the use of cheap stainless steel as the anode, the feasibility to conduct the transformation as a one-pot reaction and the proof that scaling-up these reactions is possible make this transformation attractive for potential application in industry.

Design, synthesis, and evaluation of novel coumarin-dithiocarbamate derivatives (IDs) as anti-colorectal cancer agents.

Colorectal cancer (CRC) is a common malignant tumour of human digestive tract. The high mortality rate of CRC is closely related to the limitations of existing treatments. Thus, there is an urgent need to search for new anti-CRC agents. In this work, twenty novel coumarin-dithiocarbamate derivatives (IDs) were designed, synthesized and evaluated in vitro. The results suggest that the most active compound ID-11 effectively inhibited the proliferation of CRC cell lines while shown little impact on normal colon epithelial cells. Mechanism studies revealed that ID-11 displayed bromodomain-containing protein 4 inhibitory activity, and induced G2/M phase arrest, apoptosis as well as decreased the expression levels of the key genes such as c-Myc and Bcl-2 in CRC cell lines. Moreover, the ADMET properties prediction results shown that ID-11 possess well metabolic characteristics without obvious toxicities. Our data demonstrated that compound ID-11 may be a promising anti-CRC agent and deserved for further development.

Synthesis of unsymmetrical disulfides via PPh3-mediated reductive coupling of thiophenols with sulfonyl chlorides.

A facile and rapid synthesis of unsymmetrical aryl disulfides using PPh3-mediated reductive coupling of thiophenols with aryl sulfonyl chlorides was described. Good functional group tolerance and scalability were achieved in this strategy. More importantly, the approach enables the introduction of sulfonyl chlorides into the synthesis of asymmetric organic disulfides under catalyst- and base-free conditions. Using this method, unsymmetrical aromatic disulfides could be prepared from inexpensive and readily available starting materials in moderate to excellent isolated yields, through a nucleophilic substitution pathway.

Cu(II)/Proline-Catalyzed Reductive Coupling of Sulfuryl Chloride and P(O)-H for P-S-C Bond Formation.

A considerably improved method for the Cu-catalyzed coupling of sulfuryl chloride with P(O)-H was described. Using commercially available l-proline as the ligand decreased the precatalyst loading, broadened the substrate scope and greatly promoted the efficiency of the coupling reaction. Moreover, gram-scale preparation, easy-to handle and recyclable catalyst featured this transformation.

Metal- and base-free reductive coupling reaction of P(O)-H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P-S-C bonds.

Novel and efficient synthesis of S-aryl/alkyl phosphinothioates from P(O)-H and aryl/alkyl sulfonyl chlorides under metal- and base-free conditions is described. This reaction provides an alternative strategy for the construction of P-S-C bonds in moderate to excellent yields. Moreover, this method can be readily applied to gram-scale preparation.