A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety commercially available aldehydes, along with aryl or alkyl bromides, into corresponding ketones in excellent yield. abstraction coupling technology successfully applied to expedient synthesis medicinal agent haloperidol.

Alkyl oxalates, prepared from their corresponding alcohols, are engaged for the first time as carbon radical fragments in metallaphotoredox catalysis. In this report, we demonstrate that native organic functional groups, can be readily activated with simple oxalyl chloride to become precursors a net redox-neutral Csp3–Csp2 cross-coupling broad range of aryl halides. This alcohol-activation coupling is successfully applied functionalization naturally occurring steroid and expedient synthesis...

A strategy for the installation of small alkyl fragments onto pharmaceutically relevant aliphatic structures has been established via metallaphotoredox catalysis. Herein, we report that tris(trimethylsilyl)silanol can be employed as an effective halogen abstraction reagent that, in combination with photoredox and nickel catalysis, allows a generic approach to Csp3–Csp3 cross-electrophile coupling. In this study, demonstrate variety drug-like groups successfully coupled number commercially...

The replacement of aryl rings with saturated carbocyclic structures has garnered significant interest in drug discovery due to the potential for improved pharmacokinetic properties upon substitution. In particular, 1,3-difunctionalized bicyclo[1.1.1]pentanes (BCPs) have been widely adopted as bioisosteres parasubstituted arene rings, appearing a number lead pharmaceutical candidates. However, despite value 2-substituted BCPs replacements ortho- or meta-substituted general and rapid syntheses...

Abstract Bioisosteric design has become an essential approach in the development of drug molecules. Recent advancements synthetic methodologies have enabled rapid adoption this strategy into discovery programs. Consequently, conceptionally innovative practices would be appreciated by medicinal chemistry community. Here we report expeditous method for synthesizing aryl difluoromethyl bicyclopentane (ADB) as a bioisostere benzophenone core. This involves merger light-driven C−F bond activation...

Ketones are ubiquitous in bioactive natural products, pharmaceuticals, chemical feedstocks, and synthetic intermediates. Hence, deacylative coupling reactions enable the versatile elaboration of a plethora chemicals to access complex drug candidates products. Here, we present arylation alkynylation strategies for synthesis wide range alkyl-tethered arenes alkynes from cyclic ketones methyl under dual nickel/photoredox catalysis. This reaction begins by generating pre-aromatic intermediate...

Periploside A is a pregnane hexasaccharide identified from the Chinese medicinal plant Periploca sepium, which features unique seven-membered formyl acetal bridged orthoester (FABO) motif and potent immunosuppressive activities. Here, we show synthesis of this molecule in total 76 steps with longest linear sequence 29 9.2% overall yield. The FABO constructed via combination Sinaÿ's Crich's protocol for formation glycosides, respectively. 2-deoxy-β-glycosidic linkages are assembled...

Abstract The selective functionalization of carbohydrates holds a central position in synthetic carbohydrate chemistry, driving the ongoing quest for ideal approaches to manipulate these compounds. In this study, we introduce general strategy that enables regiodivergent saccharides. use electron‐deficient photoactive 4‐tetrafluoropyridinylthio (SPyf) fragment as an adaptable activating group, facilitated efficient across all saccharide sites. More importantly, group can be directly installed...

Synthetic organic chemists continually draw inspiration from biocatalytic processes to innovate synthetic methodologies beyond existing catalytic platforms. Within this context, although 1,2-amino migration represents a viable biochemical process, it remains underutilized within the chemistry community. Here we present biomimetic accomplished through synergistic combination of mechanism and photoredox catalysis. This platform enables modular synthesis γ-substituted β-amino acids by utilizing...

Site-selective peptide functionalization provides a straightforward and cost-effective access to diversify peptides for biological studies. Among many existing non-invasive conjugations methodologies, photoredox catalysis has emerged as one of the powerful approaches site-specific manipulation on native peptides. Herein, we report highly N-termini-specific method rapidly itaconated their derivatives through combination transamination conditions. This strategy exploits facile reactivity...

The strong electron-donating ability in the photoactivated state and structural flexibility of organic anions have led to a growing interest utilizing photoexcited as reductive photocatalysts activate inert chemical bonds. Phenolate thiolate been extensively studied utilized catalysts wide range photocatalytic transformations. In contrast, employing nitrogen for radical generation received less attention despite vast possibilities designing adjusting catalyst properties. this work, we...

Nitrogen-centered radicals (NCRs) have been widely recognized as versatile synthetic intermediates for the construction of nitrogen containing molecules high value. As such, there has a long-standing interest in field organic synthesis to develop novel nitrogen-based and explore their inherent reactivity. In this study, we present generation aromatic N-heterocyclic application diverse functionalization unactivated alkenes. Bench-stable pyridinium salts were employed crucial NCR precursors,...

Aromatic oligoamide macrocycles consisting of six to ten meta-linked residues were prepared based on bimolecular coupling/cyclization a pentameric diamine and oligomeric diacid chlorides, adopt folded conformations enforced by intramolecular three-center H-bonds.

Abstract Echinoside A, a sulfonylated holostane tetrasaccharide with potent anticancer and antifungal activity, was synthesized in longest linear sequence of 35 steps 0.6 % overall yield. The synthetic approach is adaptable to the synthesis congeners analogues, as exemplified by ready ds‐echinoside A echinoside B, thus will facilitate in‐depth studies on promising biological effects A. Moreover, present demonstrates feasibility access characteristic complex triterpene glycosides that occur...

In recent years, China’s cross-border e-commerce has flourished, and the transaction volume increased year by year. Cross-border become a favorable breakthrough point for China's foreign trade. This article mainly studies action mechanism model of green supply chain based on customer behavior. Green partners select 24 secondary indicators evaluation system as input vector. The historical data each index is collected field investigation sample brought into neural network training. output...

Sustainable development integrates business, environmental, and social objectives into a unified effort to achieve common goal. customer relationship management (CRM) combines company strategy, customer-focused business processes, computer technologies. From the consumer’s perspective, it lowers psychological, energy, time, other costs; from company’s offers means of engaging with customers build lasting reliable relationships. The sustainable CRM program provides advantages businesses in...

Abstract The selective functionalization of carbohydrates holds a central position in synthetic carbohydrate chemistry, driving the ongoing quest for ideal approaches to manipulate these compounds. In this study, we introduce general strategy that enables regiodivergent saccharides. use electron‐deficient photoactive 4‐tetrafluoropyridinylthio (SPyf) fragment as an adaptable activating group, facilitated efficient across all saccharide sites. More importantly, group can be directly installed...

There is a gap between supply and demand in cross‐border e‐trading platforms. The so‐called refers to the existing good companies that cannot meet needs of buyers. Cross‐border e‐commerce, buyer’s purchase often included behavior, such as searching for goods by pressing buttons, clicking price, category other means, on‐site delivery time. It important CBEC analyze protect procurement provide seller with reference supply, so solve buyer seller. This paper mainly studies big data decision...