Chemical synthesis

  • Article
    | Open Access

    The generation of alkyl radicals through deoxygenation of abundant alcohols via photoredox catalysis is of interest. In this study, the authors report a one-pot strategy for visible-light-promoted photoredox coupling of alcohols with electron-deficient alkenes, assisted by carbon disulfide and triphenylphosphine.

    • Hong-Mei Guo
    •  & Xuesong Wu
  • Article
    | Open Access

    Enantiomeric bridged [2,2,1] bicyclic lactone skeletons and their ring-opening products are important scaffolds widely occurring in both pharmaceutics and biology active compounds. Here the authors show an efficient method for enantioselective construction of these compounds bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/ pyridinium chlorochromate oxidation.

    • Shuailong Li
    • , Zhuangxing Li
    •  & Hui Lv
  • Article
    | Open Access

    Sulfinyl radicals are an underexplored synthon in organic chemistry due to the fact that they reversibly add to pi systems and undergo homodimerization. Here the authors synthesize sulfonyl sulfones, previously thought to be unstable, and demonstrate their broad use as sulfinyl radical precursors in disulfurizations of alkenes and alkynes.

    • Zikun Wang
    • , Zhansong Zhang
    •  & Xihe Bi
  • Article
    | Open Access

    The transformation of planar aromatic molecules into non-planar structures is a challenging task and has not been realized by mechanochemistry before. Here, the authors demonstrate that mechanochemical forces can transform a planar polyarene into a curved geometry by creating new C-C bonds along the rim of the molecular structure.

    • Teoh Yong
    • , Gábor Báti
    •  & Mihaiela C. Stuparu
  • Article
    | Open Access

    2-Fluoroindoles are an important structural scaffold in many bioactive or therapeutic agents, but efficient constructions of 2-fluoroindole derivatives are very sparce. Here the authors report an efficient and general strategy for the construction of 2-fluoroindoles in which a wide variety of 2-fluoroindoles were accessed with high efficiency and chemoselectivity.

    • Jianke Su
    • , Xinyuan Hu
    •  & Qiuling Song
  • Article
    | Open Access

    Converting a carboxylic acid into a boronic acid, which makes a useful chemical handle from a feedstock chemical, currently relies on decarboxylation and requires metal catalysts and prior functionalization. Here the authors show a simplified procedure via deoxygenation, using diboron and free carboxylic acids.

    • Jianbin Li
    • , Chia-Yu Huang
    •  & Chao-Jun Li
  • Article
    | Open Access

    C-Glycosyl peptides/proteins are metabolically stable mimics of the native glycopeptides/proteins of great therapeutic potential, but their chemical synthesis is challenging. Here, the authors report a protocol for the synthesis of vinyl C-glycosyl amino acids and peptides, via a Ni-catalyzed reductive hydroglycosylation reaction of alkyne derivatives of amino acids and peptides with glycosyl bromides.

    • Yan-Hua Liu
    • , Yu-Nong Xia
    •  & Biao Yu
  • Article
    | Open Access

    Catalytic asymmetric dearomatization is a powerful tool for the rapid construction of diverse chiral cyclic molecules from cheap and easily available arenes. Here the authors show an organocatalytic enantioselective dearomatization of substituted thiophenes in the context of a rare remote asymmetric 1,10-conjugate addition.

    • Xingguang Li
    • , Meng Duan
    •  & Jianwei Sun
  • Article
    | Open Access

    Single-atom Rh catalysts present superior activity in olefins hydroformylation, yet with limited success in regioselectivity control. Here the authors develop a Rh1 single-atom catalyst with nanodiamond as support, with which good to excellent regioselectivities to branched aldehydes in hydroformylation of terminal olefins are achieved.

    • Peng Gao
    • , Guanfeng Liang
    •  & Fen-Er Chen
  • Article
    | Open Access

    The generation of non-stabilized alkyl radicals from sulfonium salts has been a challenge for several decades. Here, the authors show the treatment of S-(alkyl) thianthrenium salts, which can generate non-stabilized alkyl radicals as key intermediates that enable controlled and selective reactions under mild photoredox conditions.

    • Cheng Chen
    • , Zheng-Jun Wang
    •  & Zhuangzhi Shi
  • Article
    | Open Access

    PMOs (phosphorodiamidate morpholino oligomers) have huge potential for antisense therapy but complex and slow synthesis limits application. Here, the authors report the development of automated flow synthesis methods which reduce nucleobase coupling times from hours to minutes removing human errors and allow for high-throughput production.

    • Chengxi Li
    • , Alex J. Callahan
    •  & Bradley L. Pentelute
  • Article
    | Open Access

    Photon upconversion with near-infrared excitation and ultraviolet emission has many applications, but suffers from low quantum efficiency. Here, the authors report a six-photon upconversion process in nanoparticles with heterogeneous core-multishell structure, that regulate the energy transfer pathway.

    • Qianqian Su
    • , Han-Lin Wei
    •  & Dayong Jin
  • Article
    | Open Access

    Hydrogen atom abstraction from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs. Here the authors show a photo-induced and chemical oxidant-free cross-dehydrogenative coupling between alkanes and heteroarenes using catalytic chloride and cobalt catalyst.

    • Chia-Yu Huang
    • , Jianbin Li
    •  & Chao-Jun Li
  • Article
    | Open Access

    Homogeneous earth-abundant metal catalysis based on well-defined metal complexes is of interest for organic synthesis, but typically employs expensive catalysts, air sensitive or synthetically challenging chemicals. Here, the authors report an efficient and regio-selective catalytic system for hydroboration of vinylarenes and organic nitriles with HBPin, using commercially available CoI2 and KOtBu under ligand-free conditions.

    • Chuhan Li
    • , Shuo Song
    •  & Xiaoming Wang
  • Article
    | Open Access

    A regioselective carbosilylation of alkenes is a powerful strategy to access functionalized silylated alkanes. In this study, the authors report a catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides, mediated by tBuOK, and synthesise various silylated alkanes with tertiary or quaternary carbon centres.

    • Jun Zhou
    • , Bingyao Jiang
    •  & Norio Shibata
  • Article
    | Open Access

    Organometallic complexes have numerous applications in chemistry and biology, but diversification of their structures is synthetically challenging. Here, the authors report a versatile platform for on-the-complex annulation reactions using transient aryne intermediates to access pi-extended polypyridyl complexes.

    • Jason V. Chari
    • , Katie A. Spence
    •  & Neil K. Garg
  • Article
    | Open Access

    Great progress has been made in topochemistry of mobile oxygen anions, but metastable compounds have not yet been achieved by deintercalation of sulfur anions. Here, the authors prepare metastable oxychalcogenide phases by taking advantage of redox-reactive sulfur dimers embedded in a layered oxysulfide.

    • Shunsuke Sasaki
    • , Maria Teresa Caldes
    •  & Laurent Cario
  • Article
    | Open Access

    O-GalNAc glycans are essential in many biological and pathological processes, but difficult to access due to their structural complexity and synthetic challenges. Here, the authors report an efficient chemoenzymatic modular assembly strategy to construct structurally diverse O-GalNAc glycans, use the synthesised glycans to generate a synthetic mucin O-glycan microarray and profile binding specificities of glycan-binding proteins.

    • Shuaishuai Wang
    • , Congcong Chen
    •  & Lei Li
  • Article
    | Open Access

    Bioorthogonal diversification of peptides is generally dependent on impractical prefunctionalization methods. Here, the authors develop a manganese(I)-catalyzed C–H fluorescent labeling with BODIPY probes, which enables the development of activatable fluorophores to image cell function.

    • Nikolaos Kaplaneris
    • , Jongwoo Son
    •  & Lutz Ackermann
  • Article
    | Open Access

    Realizing ultra-high work functions (UHWFs) in hole-doped polymer semiconductors remains a challenge due to water-oxidation reactions. Here, the authors determine the role of water-anion complexes in limiting the work function and develop a design strategy for realizing UHWF polymers.

    • Qi-Mian Koh
    • , Cindy Guanyu Tang
    •  & Peter K. H. Ho
  • Article
    | Open Access

    Predictive computational approaches are fundamental to accelerating solid-state inorganic synthesis. This work demonstrates a computational tractable approach constructed from available thermochemistry data and based on a graph-based network model for predicting solid-state inorganic reaction pathways.

    • Matthew J. McDermott
    • , Shyam S. Dwaraknath
    •  & Kristin A. Persson
  • Article
    | Open Access

    Electrochemical oxidative C–C bond cleavage and functionalization are rarely developed due to the inertness and weak electronic bias of C–C bonds. In this study, the authors report the electrochemical C–C bond cleavage and 1,3-difluorination, 1,3-oxyfluorination and 1,3-dioxygenation of arylcyclopropanes under catalyst-free and external-oxidant-free conditions.

    • Pan Peng
    • , Xingxiu Yan
    •  & Aiwen Lei
  • Article
    | Open Access

    Nanographenes are emerging as a distinctive class of functional materials for electronic and optical devices. Here, the authors develop a facile strategy to recompose helicenes into a variety of chiral nanographenes through an oxidative cyclo-rearrangement reaction.

    • Chengshuo Shen
    • , Guoli Zhang
    •  & Huibin Qiu
  • Article
    | Open Access

    1-(Isoquinolin-1-yl)naphthalen-2-ol (QUINOL) is an atropisomeric heterobiaryl that serves as a platform for the synthesis of other biaryl ligands useful in asymmetric catalysis. Here, the authors report a straightforward oxidative cross-coupling reaction between isoquinolines and 2-naphthols to efficiently access the QUINOL scaffolds in a metal-free manner.

    • Peng-Ying Jiang
    • , Kai-Fang Fan
    •  & Bin Tan
  • Article
    | Open Access

    The generation of α-carbon radicals from alkoxyl radicals is challenging because 1,2-hydrogen atom transfer (HAT) is usually less favoured than 1,5-HAT. Here, the authors report a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals, enabling preparation of α-alkoxylimino alcohols and α-heteroaryl alcohols.

    • Zhaoliang Yang
    • , Yunhong Niu
    •  & Xiao Shen
  • Article
    | Open Access

    Covalent functionalization of single-walled carbon nanotubes with luminescent sp3-defects generally produces a variety of binding configurations and emission wavelengths. The authors propose a base-mediated nucleophilic functionalization approach to selectively achieve configurations for E11* and E11*- or purely E11*- defect emission.

    • Simon Settele
    • , Felix J. Berger
    •  & Jana Zaumseil
  • Article
    | Open Access

    Natural products inspire the development of pseudo-natural products through combinations of fragments of compound classes that are chemically and biologically distinct. Here, the authors report a library of 244 pseudo-natural products, evaluate them in the cell painting essays and identify the phenotypic role of individual fragments.

    • Michael Grigalunas
    • , Annina Burhop
    •  & Herbert Waldmann
  • Article
    | Open Access

    The synthesis of heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds is very attractive yet underexplored. Herein, the authors report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from biomass-derived furfuryl alcohols.

    • Xuan Liu
    • , Bo Li
    •  & Yujie Sun
  • Article
    | Open Access

    The methods for investigation of DNA-binding proteins require site-selective chemical modifications to be introduced into oligonucleotides. Here, the authors report a chemo- and regioselective method for the modification of unpaired guanosines in single- and double-stranded oligonucleotides, based on Rh(I)-carbene catalysis.

    • Yang-Ha Lee
    • , Eunsoo Yu
    •  & Cheol-Min Park
  • Article
    | Open Access

    Predicting the conversion and selectivity of a photochemical reactions is challenging. Here, the authors introduce a framework for the quantitative prediction of the time-dependent progress of a photoligation reaction and predict LED-light induced conversion through a wavelength-resolved numerical simulation.

    • Jan P. Menzel
    • , Benjamin B. Noble
    •  & Christopher Barner-Kowollik
  • Article
    | Open Access

    Machine learning algorithms offer new possibilities for automating reaction procedures. The present paper investigates automated reaction’s prediction with Molecular Transformer, the state-of-the-art model for reaction prediction, proposing a new debiased dataset for a realistic assessment of the model’s performance.

    • Dávid Péter Kovács
    • , William McCorkindale
    •  & Alpha A. Lee
  • Article
    | Open Access

    Geometric E to Z double C=C bond isomerization is challenging as it requires kinetic trapping of the Z-isomer with injection of chemical energy. Here, the authors report a dinuclear Pd(I)−Pd(I) complex that mediates selective isomerization of E-1,3-dienes to the Z-isomers without photoirradiation.

    • Eiji Kudo
    • , Kota Sasaki
    •  & Tetsuro Murahashi
  • Article
    | Open Access

    Tremendous efforts have been made over the past decades regarding the development of materials with enantioselective properties. Here, the authors present a nanostructured chiral imprinted metal alloy that exhibits high enantioselectivity and stability for the electrosynthesis of chiral molecules.

    • Sopon Butcha
    • , Sunpet Assavapanumat
    •  & Alexander Kuhn
  • Article
    | Open Access

    Alkyne metathesis catalysts usually suffer from high moisture/air sensitivity, which limit their wide applicability. Here, the authors report efficient alkyne metathesis catalysts that can operate under open-air conditions with a broad functional group tolerance.

    • Yanqing Ge
    • , Shaofeng Huang
    •  & Wei Zhang
  • Article
    | Open Access

    Due to the ionic nature of its mechanism, the Mannich reaction can only use non-enolizable aldehydes as substrates. Here, the authors expand the scope of the classical Mannich reaction to enolizable aldehydes by employing a radical process resulting in a streamlined synthesis of γ-amino-carbonyl compounds.

    • Shuai Shi
    • , Wenting Qiu
    •  & Zhankui Sun
  • Article
    | Open Access

    α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and components of biologically active small molecules. Here, the authors report an oxidant-free Rh-catalyzed electrochemical divergent vinylic C–H annulation of acrylamides with alkynes to α-pyridones and cyclic imidates.

    • Yi-Kang Xing
    • , Xin-Ran Chen
    •  & Tian-Sheng Mei
  • Article
    | Open Access

    Synthesis of peptides and proteins containing multiple disulfide bonds is challenging, limiting the elucidation of their biological functions. Here, the authors report a general synthetic strategy for fast formation of two and three disulfide bonds in peptides and proteins, and apply it to prepare several therapeutically important peptides.

    • Shay Laps
    • , Fatima Atamleh
    •  & Ashraf Brik
  • Article
    | Open Access

    Azoles are five-membered heterocycles found in peptidic natural products and synthetic peptiodomimetics. Here the authors demonstrate a posttranslational chemical modification method for in vitro ribosomal synthesis of peptides with exotic azole groups at specific positions.

    • Haruka Tsutsumi
    • , Tomohiro Kuroda
    •  & Hiroaki Suga
  • Article
    | Open Access

    Indole C-H silylation preferentially occurs at the C3 and C2 positions, while functionalization of the benzene core (C4-C7 sites) remains challenging. Here, the authors report a regioselective C7-H silylation of indole derivatives assisted by strong coordination of the palladium catalyst with a phosphorus directing group.

    • Dingyi Wang
    • , Xiangyang Chen
    •  & Zhuangzhi Shi
  • Article
    | Open Access

    Multicomponent reactions enable the rapid construction of diverse molecular scaffolds with modularity and step economy. In this work, the authors report the use of boronic acids as carbon nucleophiles in a Passerini-type three-component coupling reaction towards an expanded inventory of α-hydroxyketones.

    • Kai Yang
    • , Feng Zhang
    •  & Qiuling Song
  • Article
    | Open Access

    The gem-difluoroalkene functionality is relevant to drug design as it is a bioisostere of a carbonyl group. Here, the authors report the synthesis of 2,2-difluorovinyl benzoates as versatile building blocks for modular synthesis of gem-difluoroenol ethers and gem-difluoroalkenes by nickel-catalyzed cross coupling.

    • Bingnan Du
    • , Chun-Ming Chan
    •  & Wing-Yiu Yu
  • Article
    | Open Access

    Ammonia and nitric acid are key platform chemicals to introduce nitrogen into organic molecules, however gaseous N2 would be a more direct and available source of nitrogen. Here, the authors report a direct catalytic nitrogenation to afford valuable arylamines and N-heterocycles from organohalides using dinitrogen (N2) as the nitrogen source.

    • Kai Wang
    • , Zi-Hao Deng
    •  & Zhang-Jie Shi