Electrochemical Oxidative (4 + 2) Cyclization of Anilines and o-Phenylenediamines for the Synthesis of Phenazines.

Phenazines, crucial constituents of nitrogen-containing heterocycles, widely exist in functional compounds. Herein, we report an anodic oxidative (4 + 2) cyclization between anilines and o-phenylenediamines for the uniform construction of phenazines in a simple undivided cell. Dual C-H amination followed by oxidation represents an outstanding step and atom efficiency. A sequence of phenazines is produced with excellent functional group tolerance at room temperature.

Electro-oxidative three-component cascade coupling of isocyanides with elemental sulfur and amines for the synthesis of 2-aminobenzothiazoles.

2-Aminobenzothiazoles are commonly encountered in various functional compounds. Herein, we disclose an electro-oxidative three-component reaction for the effective synthesis of 2-aminobenzothiazoles under mild conditions, utilizing non-toxic and abundant elemental sulfur as the sulfur source. Both aliphatic amines and aryl amines demonstrate good compatibility at room temperature, highlighting the broad functional group tolerance of this approach. Additionally, elemental selenium demonstrated reactivities comparable to those of elemental sulfur.

Photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access 2,4-disubstituted quinolines.

We herein report an efficient photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access a wide range of 2,4-disubstituted quinolines. Preliminary mechanism experiment results suggested that this reaction was initiated by an acyl radical generated from acyl chlorides through a single-electron-transfer (SET) process. This transformation showed good substrate suitability and functional group compatibility at room temperature.

[Effects of adhesive and primer on the bonding strength of zirconia to resin cement].

OBJECTIVE: This study aimed to compare the effects of water storage treatment and thermal cycling on the shear bond strength (SBS) of three self-adhesive dual-cure resin cements. METHODS: Six cubic zirconia specimens with side length of 2 cm were obtained by cutting and sintering. Three self-adhering dual-cure resin cements (i.e., Clearfil SAC, RelyX U200, and Multilink Speed) were selected. According to their bonding modes, they were divided into three groups: direct bonding group (direct coating with resin cement), adhesive group (applying universal adhesives and then coating with resin cement), and primer group (applying Z-Prime Plus and then coating with resin cement). According to experimental conditions, each group was divided into two subgroups: subgroup a (water storage at 37 ℃ for 24 h) and subgroup b (thermalcycling for 5 000 times). SBS data were analyzed by one-way ANOVA by using SPSS 19.0 software (P<0.05). The fractured zirconia surface was observed under a stereomicroscope. RESULTS: After water storage for 24 h, the SBS of the adhesive group and the primer group of the three resin cements was higher than that of the direct adhesive group (P<0.05), but the difference in SBS between the adhesive group and the primer group was not significant (P>0.05). After thermalcycling, the SBS of the three types of resin cements decreased (P<0.05); the SBS of the adhesive group was higher than that of the direct adhesive group and the primer group (P<0.05). Fracture mode analysis revealed that the type Ⅲ fracture mode evidently increased after the thermalcycling treatment compared with the water storage treatment. CONCLUSIONS: The universal adhesives and the primer can improve the SBS of self-adhesive dual-cure resin cement in water storage at 37 ℃ for 24 h. The universal adhesives had a better bonding durability than the zirconia primer.

Competing Dehalogenation versus Borylation of Aryl Iodides and Bromides under Transition-Metal-Free Basic Conditions.

In this work, selectivity-controllable base-promoted transition-metal-free borylation and dehalogenation of aryl halides are described. Under the conditions of borylation, the dehalogenation which emerges as a competitive side reaction has been well-controlled by carefully controlling the borylation conditions. On the other hand, the dehalogenation using benzaldehyde as a hydrogen source has also been accomplished. The applications of direct radical borylation and dehalogenation of aryl halides demonstrate their synthetic practicability in pharmaceutical-oriented organic synthesis. Based on the experimental evidences, the tBuOK/1,10-Phen-triggered radical nature of both competitive reactions has been revealed.

Copper-catalyzed oxidative benzylic C-H cyclization via iminyl radical from intermolecular anion-radical redox relay.

Base-promoted C-H cleavage without transition metals opens a practical alternative for the one based on noble metals or radical initiators. The resulting carbanion can pass through radical addition to unsaturated bonds like C-N or C-C triple bonds, in which stoichiometric oxidants are needed. When in situ C-H cleavage meets catalytic carbanion-radical relay, it turns to be challenging but has not been accomplished yet. Here we report the combination of base-promoted benzylic C-H cleavage and copper-catalyzed carbanion-radical redox relay. Catalytic amount of naturally abundant and inexpensive copper salt, such as copper(II) sulfate, is used for anion-radical redox relay without any external oxidant. By avoiding using N-O/N-N homolysis or radical initiators to generate iminyl radicals, this strategy realizes modular synthesis of N-H indoles and analogs from abundant feedstocks, such as toluene and nitrile derivatives, and also enables rapid synthesis of large scale pharmaceuticals.