Comparative skin histological and transcriptomic analysis of Rana kukunoris with two different skin colors.

This study compares the skin structures of Rana kukunoris with two different skin colors living in the same area of Haibei in the Northeastern Qinghai-Tibet Plateau. The skin thickness of the khaki R. kukunoris was significantly greater than that of the brown R. kukunoris (P < 0.01), and significantly more mucous and granular glands were present on the dorsal skin of the khaki frog (P < 0.05). Meanwhile, the melanocytes on the dorsal skin of the brown frog were significantly larger than those on the khaki one (P < 0.05). Morphological changes in the expansion and aggregation of melanocytes seemed to deepen the skin color of R. kukunoris. Moreover, transcriptome sequencing identified tyrosine metabolism, melanogenesis, and riboflavin metabolism as the main pathways involved in melanin formation and metabolism in brown R. kukunoris. TYR, MC1R was upregulated as the skin color of R. kukunoris was deepened and contributed to melanin production and metabolism. In contrast, the khaki frog had significantly more upregulated genes and metabolic pathways related to autoimmunity. The khaki frog appeared to defend against ultraviolet (UV) radiation-induced damage by secreting mucus and small molecular peptides, whereas the brown frog protected itself by distributing a large amount of melanin. Hence, the different skin colors of R. kukunoris might represent different adaptation strategies for survival in the intense UV radiation environment of the Qinghai-Tibet Plateau.

Palladium-Catalyzed Asymmetric Dearomative Carbonylation of Indoles.

Herein, we disclose a strategy for the asymmetric dearomatization of N-arylacyl indoles via a palladium-catalyzed tandem Heck/carbonylation, leading to an array of indoline-3-carboxylates bearing vicinal C2-aza-quaternary and C3 tertiary stereocenters in high yields and excellent enantio- and diastereoselectivities. This study is an important advance in the field of asymmetric carbonylation and enantioselective dearomatization reactions.

Constructing chiral bicyclo[3.2.1]octanes via palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes.

Transition-metal-catalyzed tandem Heck/carbonylation reaction has emerged as a powerful tool for the synthesis of structurally diverse carbonyl molecules, as well as natural products and pharmaceuticals. However, the asymmetric version was rarely reported, and remains a challenging topic. Herein, we describe a palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes. Alcohols, phenols and amines are employed as versatile coupling reagents for the construction of multifunctional chiral bicyclo[3.2.1]octanes with one all-carbon quaternary and two tertiary carbon stereogenic centers in high diastereo- and enantioselectivities. This study represents an important progress in both the asymmetric tandem Heck/carbonylation reactions and enantioselective difunctionalization of internal alkenes.

Palladium-Catalyzed Asymmetric Intramolecular Reductive Heck Desymmetrization of Cyclopentenes: Access to Chiral Bicyclo[3.2.1]octanes.

A palladium-catalyzed asymmetric reductive Heck reaction of unactivated aliphatic alkenes, with eliminable ß-hydrogen atoms, has been realized for the first time. A series of optically active bicyclo[3.2.1]octanes bearing chiral quaternary and tertiary carbon stereocenters were obtained in good yields with excellent enantioselectivities, exhibiting good functional-group tolerance and scalability. Moreover, deuterated optically active bicyclo[3.2.1]octanes were also obtained in high efficiency.

Redox-Neutral Atom-Economic Pd(0)-Catalyzed Dearomatization of ß-Naphthols with Alkynes toward Naphthalenones.

A dearomative coupling of ß-naphthols with alkynes via Pd hydride catalysis has been developed. This redox-neutral strategy provides a straightforward platform to access diverse naphthalenones bearing congested quarternary stereocenters with excellent atom and step economy since no leaving groups are needed to preinstall on the allylic reagents. The overall utility of this protocol is exemplified by broad functional group compatibility and gram-scale capacity.