Organocatalytic (Z/E)-Selective Synthesis of 3-Vinylnaphthofurans via a Formal (3 + 2) Cycloaddition.

A formal (3 + 2) cycloaddition of 1,4-enediones with 2-naphthols was established under the catalysis of trifluoromethanesulfonic acid as an organocatalyst, leading to the efficient synthesis of structurally diverse 3-vinylnaphthofurans with high yields and excellent (Z/E)-selectivities (up to 96% yield, all >20:1 Z/E). This formal (3 + 2) cycloaddition involved a cascade reaction process, and the intramolecular hydrogen bond in the structure of 3-vinylnaphthofurans should play an important role in controlling the (Z/E)-selectivity of the newly formed vinyl group. Moreover, this class of 3-vinylnaphthofurans was discovered to have an axial chirality. This work provides an organocatalytic approach for constructing multi-substituted vinylnaphthofurans via a cascade reaction with excellent control of the (Z/E)-selectivity, which will serve as a useful strategy for synthesizing vinylnaphthofurans via in situ construction of the furan core and formation of the vinyl group.

3D Printing of Polydiacetylene Photocomposite Materials: Two Wavelengths for Two Orthogonal Chemistries.

Polydiacetylene (PDA) materials are appealing and gaining increasing research interest due to their outstanding chromatic transition and fluorescence enhancement effects upon exposure to various environmental stimuli. However, despite the photomask method, there are very few reports about the spatial controllable photopolymerization and subsequent 3D printing of PDA until now. Herein, for the first time, we reported the preparation of PDA photocomposite materials based on polyacrylate through the strategy of dual-wavelength polymerization and orthogonal chemistry. First, diacetylene (DA) monomers were homogeneously dispersed in acrylate resin. Then a violet light emitting diode (LED) (or laser diode) was used for the free radical polymerization of polyacrylate. Finally, UV irradiation was utilized to induce the 1,4-topopolymerization of PDA, which could show a successive blue to purple to red color transition in response to the gradient increment of temperature. Interestingly, instead of photomasks, we applied a 3D printing approach directly to this composite material and fabricated some macroscopic stereo patterns, which also illustrated thermochromic properties. This novel kind of functional photocomposite material would demonstrate a huge application prospect in many potential fields, including colorimetric sensing, information encryption, anticounterfeiting, and so on.