By the acid-catalyzed [2 + 2] condensation, an unprecedented neo-N-confused phlorin (neo-NCphlorin 1) was successfully synthesized. By treating 1 with N-chlorosuccinimide, the corresponding chloro-substituted neo-NCphlorin (1-Cl) was obtained. The oxidization of 1 with FeCl afforded the neo-N-confused phlorinone (neo-NCphlorinone 2), which bears a relatively coplanar conformation, different from the highly distorted ones observed for 1 and 1-Cl. Notably, 2 shows striking long-wavelength absorption beyond 1300 nm upon addition of TBAF.
By oxidation of an alternately N-confused bilane in CH 2 Cl 2 , a C−N fused tetrapyrrin was synthesized that bears a 5.5.5-tricyclic ring generated from an intramolecular C−N linkage. When CH 3 CN was used as the reaction medium, a multiply C−N-fused octapyrrolic dimer was also obtained that contained two 5.5.5.7.5-pentacyclic moieties and a bipyrrole unit generated from the intramolecular C−N linkage and intermolecular C−C linkage, respectively. This could be coordinated with Ni(acac) 2 to afford a mixed-ligand complex.
A novel approach for synthesizing the key dolutegravir intermediate is described via MgBr2-promoted intramolecular cyclization. Condensation of commercially available methyl oxalyl chloride and ethyl 3-(N,N-dimethylamino)acrylate afforded the vinylogous amide in an excellent yield. Subsequent substitution by aminoacetaldehyde dimethyl acetal and methyl bromoacetate gave rise to the expected precursor for cyclization, which was promoted by MgBr2 to highly selectively convert into pyridinone diester. The key dolutegravir intermediate was finally prepared by the selective hydrolysis of the corresponding diester via LiOH.
Novel meso-meso directly linked porphyrin hybrids were successfully targeted and synthesized, with porphyrin units linked with dipyrrin, bidipyrrin or thiacorrole, expanding the ranges of dipyrrin derivatives and showing diverse metal coordinations and further influencing the chemical shift of pyrrole units. The porphyrinyl dipyrrin nickel complex 3 was successfully obtained in a high yield by the oxidation of porphyrinyl dipyrromethane 2 and subsequent coordination. Further oxidative coupling reactions of 3 afforded por-bidipyrrin-por hybrid 4. Interestingly, an unexpected methoxy por-bidipyrrin-por hybrid 6 was generated by treating 4 with FeCl3 in CH2Cl2/MeOH and subsequent coordination. In addition to open chain hybrids, an aromatic scaffold hybrid por-thiacorrole-por 8 was synthesized by treating porphyrinyl dibromo-dipyrrin nickel complex 7 with Na2S·9H2O. A series of porphyrin hybrids offers a new approach for π-conjugated molecules.
Facial reenactment has developed rapidly in recent years, but few methods have been built upon reenacted face in videos. Facial-reenacted emotion synthesis can make the process of facial reenactment more practical. A facial-reenacted emotion synthesis method is proposed that includes a dual-path generative adversarial network (GAN) for emotion synthesis and a residual-mask network to impose structural restrictions to preserve the mouth shape of the source person. To train the dual-path GAN more effectively, a learning strategy based on separated discriminators is proposed. The method is trained and tested on a very challenging imbalanced dataset to evaluate the ability to deal with complex practical scenarios. Compared with general emotion synthesis methods, the proposed method can generate more realistic facial emotion synthesised images or videos with higher quality while retaining the expression contents of the original videos. The DualPathGAN achieves a Fréchet inception distance (FID) score of 9.20, which is lower than the FID score of 11.37 achieved with state-of-the-art methods.This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Oxidation of neo-N-confused phlorin 1 with excessive FeCl leads to regioselective ring opening, generating three linear tetrapyrroles, i.e., (10 Z,15 Z)-biladienone 2, (10 Z,15 E)-biladienone 3, and 19-methoxy (10 Z,15 E)-biladiene 4 with an overall yield of 88%. The coordination of these compounds with Zn(II) is affected by the inverted terminal pyrrolic unit, and the presence of the electron-withdrawing keto moiety. The structural identities were also clearly elucidated by the crystal structures of 3 and 4-Zn and were rationalized by DFT calculations.
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