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The intensive interest in expanded porphyrins can be attributed to their appealing photoelectric and coordination behavior. In this work, an N‐confused heptaphyrin 1 was synthesized by an acid‐catalyzed [3+4] condensation reaction. The introduction of an N‐confused pyrrolic unit into the heptaphyrin macrocycle led to the formation of a figure‐eight‐like conformation with nonsymmetrical "NNNN" and "NNNC" coordination cavities employable for bimetallic coordination. As a result, chelation of 1 with Zn(II) and Cu(II) afforded mono‐Zn(II) complex 2 and bis‐Cu(II) complex 3, respectively, with the metal atoms exhibiting distorted square‐planar geometries. In complex 3, an oxygen atom is attached to the α‐C atom of N‐confused pyrrole D, and thus the N and C atoms of ring D participate in coordination within the two cavities. Interestingly, treatment of 1 with Cs2CO3 in MeOH resulted in regioselective substitution of all the seven para‐F atoms in the meso‐C6F5 groups as well as the α‐H of ring D by eight methoxy moieties. Complex 3 displays a red‐shifted absorption band edge of ca. 2200 nm, compared to that of ca. 1600 nm observed for 1. This work provides an example of incorporating an N‐confused pyrrole to construct expanded porphyrins with distinctive coordination behavior and tunable NIR absorption. [ABSTRACT FROM AUTHOR]

A catalytic asymmetric vinylogous aldol reaction between β,γ-unsaturated amides and isatins has been developed. In the presence of 10 mol% of tertiary amine-thiourea C7, the vinylogous reaction has been achieved in up to 98% yield and up to 99% ee (26 examples). This methodology provides an efficient approach to construct chiral multifunctional 3-hydroxy-2-oxindoles. Moreover, the transformations of the chiral products, including the esterification of amides, the hydrogenation of the C–C double bond and further conversion to spirolactones, have been investigated. [ABSTRACT FROM AUTHOR]

CF3-substituted imidoyl sulfoxonium ylides (TFISYs) are extraordinarily versatile and powerful synthons for use in cyclization chemistry that affords diverse CF3-substituted N-heterocycles. We first reacted TFISYs as a two-atom synthon with readily available azoalkenes and then subjected the products to metal-free formal (4+2) cycloaddition chemistry. This protocol features mild conditions and broad substrate scope, is simple to operate, and provides highly functionalized trifluoromethylpyridazines that are widely found in bioactive molecules. [ABSTRACT FROM AUTHOR]

According to the current situations of cosmetics industry and raw material development in China, the gaps and potential advantages for development of cosmetics industry were analyzed, and especially, the development and innovation of raw materials were compared between China and those developed countries. Based on the successful application of the theory of pharmacophylogeny in development of traditional Chinese medicine and traditional Chinese medicine resources, it was proposed that, taking the theory of pharmacophylogeny as the guidance, China's rich plant resources and traditional medicine advantages should be utilized, and new ideas and implementation paths for development of new cosmetic plant raw materials should be explored. That would be of great significance to expand the sources of utilizable cosmetic plant raw materials, guide the search and development of new plant raw materials for cosmetics, look for alternatives to foreign raw materials and provide warning to plant raw materials of potential risk. It could provide effective support for rapidly improving the scientific and technological innovation power of China's cosmetics and achieving highquality industrial development. [ABSTRACT FROM AUTHOR]