Mechanical property-enhanced thermally conductive self-healing composites: preparation using designed self-healing matrix phase and hyBNNSs.

Polymer composites with good thermal conductivity are gaining more and more attention in the current electronics sector, due to their superior heat management capabilities. However, conventional thermally conductive polymer composites are usually subject to interruptions in heat transfer because of physical damage. The present study prepared mechanical property-enhanced thermally-conductive self-healing composites through compositing a self-healing polyurethane matrix with hydroxylated boron nitride (hyBNNSs). The self-healing polyurethane was obtained by incorporating ligands and cerium(III) triflate [Ce(SO3CF3)3] as the metal center into the polyurethane elastomer. An optimal sample (PUp2C) with high tensile strength (6.8 MPa) and stretchability (1053%), ideal toughness (49.2 MJ m-3), and remarkable healing efficiency (97% healing after 48 h at 35 °C) was obtained. An increase in the content of hyBNNSs from 10% to 30% led to a significant increase in the mechanical performance of hyBNNSs20%/PUp2C, which manifested as the increase in the elongation at break (from 1053% to 1302.5%) and stress (from 6.8 MPa to 16.4 MPa). The XRD results revealed that combining PU with hyBNNSs through coordination bonds could significantly promote the crystallization of PUp2C, which was beneficial to enhancing the mechanical properties of the composites. The through-plane (λ⊥) and the in-plane (λ∥) values of the BNNSs30%/PUp2C composite reached 0.41 and 1.42 W mK-1, respectively, which were 195.2% and 507.1% higher than those of the original PUp2C, respectively.

Synthesis of (E,E)-Dienones and (E,E)-Dienals via Palladium-Catalyzed γ,δ-Dehydrogenation of Enones and Enals.

A new strategy for the synthesis of conjugated (E,E)-dienones and (E,E)-dienals via a palladium-catalyzed aerobic γ,δ-dehydrogenation of enones and enals has been developed. The method can be employed in the direct and efficient synthesis of various (E,E)-dienones and (E,E)-dienals, including non-substituted α-, ß-, and γ- and/or δ-substituted (E,E)-dienones and (E,E)-dienals. The protocol is featured by the ready accessibility and elaboration of the starting materials, good functional group compatibility, and mild reaction conditions. Furthermore, the reaction is of complete E,E-stereoselectivity and uses molecular oxygen as the sole clean oxidant.

Dehydrogenative ß-Arylation of Saturated Aldehydes Using Transient Directing Groups.

An unprecedented cross-dehydrogenative-coupling (CDC) reaction of saturated aldehyde ß-C-H with arenes to form cinnamaldehydes via the cleavages of four C-H bonds has been developed. The reaction possesses complete E-stereoselectivity for the C═C double bond. The protocol is featured by atom and step economy, mild reaction conditions, and convenient operation.

Direct Dehydrogenative Arylation of Benzaldehydes with Arenes Using Transient Directing Groups.

The utilization of the transient directing strategy into the direct oxidative dehydrogenative arylation of aldehydes with arenes was reported for the first time. Featured by mild reaction conditions, good functional group compatibility, and great regioselectivity, the method should find broad applications in new medicine and material development and discovery processes.

Synthesis of Hydrazines via Radical Generation and Addition of Azocarboxylic tert-Butyl Esters.

A new chemistry of azo compounds that is a radical generation and addition in situ of azocarboxylic tert-butyl esters to synthesize hydrazines has been described. The protocol provides a novel strategy for the synthesis of various hydrazines. The advantages of the transformation include broad substrate scope, benign conditions, and convenient operation.

Synthesis of Difluoromethylthioesters from Aldehydes.

Difluoromethylthioester compounds are yet another important kind of organofluorine compound and are reported here for the first time. They can be efficiently synthesized from various aldehydes. The synthetic method features mild reaction conditions, good tolerance of functional groups, broad substrate scope, and importantly, no metal is involved in the reaction. The approach has the potential to become an important tool for the late-stage functionalization of advanced synthetic intermediates, and should have many applications in medicinal chemistry.

Synthesis of 6H-Benzo[c]chromenes via Palladium-Catalyzed Intramolecular Dehydrogenative Coupling of Two Aryl C-H Bonds.

The palladium-catalyzed intramolecular C-H/C-H coupling reaction of two simple arenes to generate 6H-benzo[c]chromenes has been reported for the first time. The approach features broad substrate scope and good tolerance of functional groups and uses molecular oxygen as the terminal oxidant. The high efficiency of the approach is verified by concise total synthesis of natural product cannabinol.

Palladium-Catalyzed C-H Functionalization of Phenyl 2-Pyridylsulfonates.

An efficient palladium(II)-catalyzed intermolecular direct ortho-alkenylation and acetoxylation of phenols has been developed. The reaction proceeded via a seven-membered cyclopalladated intermediate and showed complete regio- and diastereoselectivity. The approach also provided an efficient route for the synthesis of coumarins and benzofurans.