Reaction mechanisms articles within Nature Communications

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  • Article
    | Open Access

    Vicinal dicarbofunctionalization (DCF) reactions of alkenes have been extensively explored in ionic chemistry but the enantioselective radical mediated version of DCF remains largely unexplored. Here, the authors demonstrate a radical vicinal DCF reaction of olefins by merging of radical addition and cross-coupling using photoredox and copper dual catalysis.

    • Peng-Zi Wang
    • , Yuan Gao
    •  & Jia-Rong Chen

  • Article
    | Open Access

    Bicyclo[1.1.1]pentanes (BCPs) are important motifs in contemporary drug design, however, approaches to BCPs featuring adjacent stereocenters are rather limited. Here, the authors report a photo- and organocatalyzed asymmetric addition of simple aldehydes to [1.1.1]propellane to generate enantioenriched α-chiral BCPs.

    • Marie L. J. Wong
    • , Alistair J. Sterling
    •  & Edward A. Anderson

  • Article
    | Open Access

    Vibrational strong coupling controls the ground-state reactivity of molecules in optical cavities, but the underlying theory is still elusive. The authors analyze a molecular system coupled to a cavity mode and find that the reaction rate is suppressed for a particular cavity frequency, related to the topology of the reaction barrier region, analogously to a solvent caging effect.

    • Xinyang Li
    • , Arkajit Mandal
    •  & Pengfei Huo

  • Article
    | Open Access

    Metal carbene is usually employed as a 1-carbon synthon or 3-carbon synthon in a variety of cycloaddition reactions. Here, the authors report a gold-catalyzed cascade protocol for the assembly of polycarbocyclic frameworks via a β-aryl gold-carbene intermediate which reacts as a 4-carbon synthon with alkenes in [4 + 2]-cycloadditions.

    • Cheng Zhang
    • , Kemiao Hong
    •  & Xinfang Xu

  • 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

    Spin polarization is at the basis of quantum information and underlies some natural processes, but many aspects still need to be explored. Here, the authors, by quantum mechanical computations, show that even a weak spin-orbit coupling near a conical intersection can induce large spin selection, with consequences for spin manipulation in photochemical or electrochemical reactions.

    • Yanze Wu
    •  & Joseph E. Subotnik

  • 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

    Metal-free olefin diamination may display challenges, especially when targeting fluorinated amines. Here, the authors report a double nucleophilic functionalization of an activated alkene originated from a trifluoropropenyliodonium salt with two nucleophiles for the selective synthesis of trifluoromethylated ethylene amines and diamines.

    • Ferenc Béke
    • , Ádám Mészáros
    •  & Zoltán Novák

  • Article
    | Open Access

    Skeletal reorganizations are intriguing processes in chemical synthesis due to their mechanism, atom-economy and synthetic versatility. Herein, the authors describe a divergent skeletal reorganization of N-sulfonyl ynamides to thiete sulfones and propargyl sulfonamides.

    • Linwei Zeng
    • , Yuxin Lin
    •  & Sunliang Cui

  • Article
    | Open Access

    Development of algorithms to predict reactant and reagents given a target molecule is key to accelerate retrosynthesis approaches. Here the authors demonstrate that applying augmentation techniques to the SMILE representation of target data significantly improves the quality of the reaction predictions.

    • Igor V. Tetko
    • , Pavel Karpov
    •  & Guillaume Godin

  • Article
    | Open Access

    Despite of the high demand of chiral allenes, their asymmetric synthesis remains a challenge for organic chemists. Here, the authors report a stereodivergent synthesis of trisubstituted allenes via asymmetric additions of oxazolones to activated 1,3-enynes enabled by modification of chiral phosphoric acid catalysts.

    • Jiawen Wang
    • , Sujuan Zheng
    •  & Xiaoyu Yang

  • Article
    | Open Access

    Thiols are important precursors for the synthesis of a variety of pharmaceutically important sulfur-containing compounds. Here, the authors report a visible light-mediated decarboxylative thiolation of alkyl redox-active esters to free thiols and the in situ product diversification of a number of thiol derivatives.

    • Tianpeng Cao
    • , Tianxiao Xu
    •  & Saihu Liao

  • Article
    | Open Access

    Alkyl carboxylic acids and primary amines are ubiquitous and useful for synthesis of new compounds. Here, the authors report a manganese-mediated reductive decarboxylative/deaminative functionalization of activated aliphatic acids and primary amines for construction of C-C and C-X bonds under mild conditions.

    • Zhan Li
    • , Ke-Feng Wang
    •  & Honggen Wang

  • Article
    | Open Access

    The mechanical degradation of polymers is typically limited to a single chain scission event and the loss of stress transfer during the scission process limits the extent of degradation achieved. Here, the authors report a mechanically triggered, delayed scission strategy that allows many eventual scission events to be initiated within a single polymer chain.

    • Yangju Lin
    • , Tatiana B. Kouznetsova
    •  & Stephen L. Craig

  • Article
    | Open Access

    Halogen bonding (HB) catalysis is rapidly gaining momentum, however, cases of XB activation for challenging bonds formation are rare. Here, the authors show a robust XB catalyzed 2-deoxyglycosylation with broad scope and featuring a quantum tunneling phenomenon in the proton transfer rate determining step.

    • Chunfa Xu
    • , V. U. Bhaskara Rao
    •  & Charles C. J. Loh

  • Article
    | Open Access

    Cyclic amines are commonly present in natural products and synthetic compounds, but methods for their skeletal diversification are limited. Here, the authors report a strategy for selective ring-opening functionalization of unstrained cyclic amines to pluripotent products that can be further diversified.

    • Youyoung Kim
    • , Joon Heo
    •  & Sangwon Seo

  • Article
    | Open Access

    Metal-carbon and carbon-carbon triple bonds are highly unsaturated bonds and their reactions tend to afford cycloaddition intermediates or products. Here, the authors report a new robust reaction on metal-carbon and carbon-carbon triple bonds which affords region- and stereospecific acyclic addition products.

    • Shiyan Chen
    • , Longzhu Liu
    •  & Haiping Xia

  • Comment
    | Open Access

    After two decades of steady growing, symbiotic merger of organocatalysis with emerging electrochemical and photochemical tools are envisioned as hot topics in the coming decade. Here, these trends are discussed in parallel to the implementation of artificial intelligence-based technologies, which anticipate a paradigm shift in catalyst design.

    • José M. Lassaletta

  • Article
    | Open Access

    The geometric phase effect associated with a conical intersection between the ground and first excited electronic state has been predicted in the H3 system below the conical intersection energy. The authors, by a crossed molecular beam technique and quantum dynamic calculations, provide experimental evidence and insight into its origin.

    • Daofu Yuan
    • , Yin Huang
    •  & Xueming Yang

  • Article
    | Open Access

    Flavins and deazaflavins are well suited for photoredox processes but their application in photoreductions is challenging. Here, the authors provide direct evidence of the high reductive power of excited deazaflavin semiquinones and their application in catalytic photodehalogenations.

    • Andreas Graml
    • , Tomáš Neveselý
    •  & Burkhard König

  • Article
    | Open Access

    Cross-coupling processes without the use of transition metals are challenging to achieve. Here, the authors show a transition-metal-free cross-coupling utilizing aryl(heteroaryl) methyl sulfoxides and alcohols to afford alkyl aryl(heteroaryl) ethers and propose a nucleophilic addition mechanism based on experiments and theory.

    • Guolin Li
    • , Yexenia Nieves-Quinones
    •  & Tiezheng Jia

  • Article
    | Open Access

    Dioxolenium ion intermediates formed from remote positions are hypothesized to direct stereoselective glycosylations. Herein we combine infrared ion spectroscopy, DFT calculations and synthetic work to characterize and study these dioxolenium ions and their role in stereoselective glycosylation reactions.

    • Thomas Hansen
    • , Hidde Elferink
    •  & Thomas J. Boltje

  • Article
    | Open Access

    The formation of chiral molecules generally relies on direct chirality transfer from catalyst to products. Here, the authors report a strategy based on point chirality transfer from the catalyst to a dirhodium carbene intermediate with axial chirality, which is then transferred to products via C(sp2)-H functionalization.

    • Kuiyong Dong
    • , Xing Fan
    •  & Xinfang Xu

  • Article
    | Open Access

    Diatomic carbon (C2) is historically an elusive chemical species, considered to require high physical energy for its generation. Here, the authors describe the first room-temperature chemical synthesis of C2 and present experimental evidence for its singlet biradical (quadruple bonding) character and role as a molecular element of nanocarbons.

    • Kazunori Miyamoto
    • , Shodai Narita
    •  & Masanobu Uchiyama

  • Article
    | Open Access

    C-N bond forming is an established strategy to form amines, which are quintessential in chemical synthesis and in nature. Here, the authors report three classes of photoredox reactions, involving C(sp3)-N coupling between N-centered radicals and alkyl radicals and C(sp3)- C(sp3) coupling via C(sp3)-H alkylation.

    • Quanping Guo
    • , Qiang Peng
    •  & Zhaoqing Xu

  • Article
    | Open Access

    Traditional synthesis of stereodefined piperidines requires selective installation of functional groups that can lower efficiency and modularity. Here, the authors assemble stereochemically complex and highly substituted dehydropiperidines via an intermolecular ring expansion between bicyclic aziridines and Rh-supported vinyl carbenes.

    • Josephine Eshon
    • , Kate A. Nicastri
    •  & Jennifer M. Schomaker

  • Article
    | Open Access

    Trifluoromethyl ethers are important bioactive targets in pharmaceuticals and agrochemicals, however, their synthesis is often not straightforward. Here, the authors disclose a reagent for the nucleophilic trifluoromethoxylation of alkyl halides without silver and under mild conditions.

    • Yan Li
    • , Yang Yang
    •  & Pingping Tang

  • Article
    | Open Access

    Supramolecular catalytic assemblies attract enormous interest due to their activity that rivals natural enzymes. Using ab initio molecular dynamics, the authors show that a gold catalyst in a Ga4L612- nanocage, while impeded by reorganization energy, is accelerated by hosting a catalytic water molecule.

    • Valerie Vaissier Welborn
    • , Wan-Lu Li
    •  & Teresa Head-Gordon

  • Article
    | Open Access

    Fluorinated or fluoroalkylated allenes are versatile building blocks for medicinal and material chemistry. Here, the authors show a regioselective trifunctionalization of 1,3-enynes proceeding through double C-F bond formation and concomitant installation of a -NSO2Ph group to the allene moiety.

    • Munira Taj Muhammad
    • , Yihang Jiao
    •  & Hongli Bao

  • Article
    | Open Access

    Sonogashira cross-coupling is a powerful strategy to prepare functionalized internal alkynes. Here, the authors report a domino sequence for the generation of γ-/δ-alkynyl nitriles and γ-alkynyl ketones from the coupling of terminal alkynes with O-acyloximes derived from cycloalkanones and acylic ketones, respectively.

    • Zhaodong Li
    • , Rubén O. Torres-Ochoa
    •  & Jieping Zhu

  • Article
    | Open Access

    Feshbach resonances are transiently trapped states along a reaction coordinate, providing a probe to the reaction’s potential energy surface (PES) but difficult to analyze in polyatomic systems. Here the authors identify Feshbach resonances in a reacting 4-atom system by state-to-state quantum dynamics using a full-dimensional PES.

    • Xiaoren Zhang
    • , Lulu Li
    •  & Dong H. Zhang

  • Article
    | Open Access

    Structural diversity of organic fluorophores is of importance for several applications (fluorescent markers, photosensitizers, etc.). Here the authors report a method to merge radical chemistry with C–H activation to construct a brand-new class of flavylium fluorophores starting from (hetero)aryl ketones and alkynes.

    • Jiangliang Yin
    • , Yuming Zhang
    •  & Jingsong You

  • Article
    | Open Access

    Hyperconjugative aromaticity combines the concepts of hyperconjugation and aromaticity and explains cyclopentadiene stability. Here, the authors demonstrate extended hyperconjugative aromaticity in a metallated indole ring, which shows extended electron conjugation due to the dual hyperconjugation.

    • Kui Xiao
    • , Yu Zhao
    •  & Liang Zhao

  • Article
    | Open Access

    Understanding the dynamic evolution of the catalysts’ structure under reaction conditions is crucial in heterogeneous catalysis. Here the authors use ab initio molecular dynamics simulations to show an anomalous decrease in reaction free energies and barriers on dynamical sub-nanometer Au clusters supported on MgO(001).

    • Juan-Juan Sun
    •  & Jun Cheng

  • Article
    | Open Access

    Difluorocarbene is a versatile and efficient intermediate for fluorine incorporation. Here, the authors show that difluorocarbene can be oxidized to carbonyl fluoride and this process is confirmed in 18O-trifluoromethoxylation reactions, by observation of AgOCF3 species and theory.

    • Jiao Yu
    • , Jin-Hong Lin
    •  & Ji-Chang Xiao

  • Article
    | Open Access

    Nucleophiles cannot be directly reacted with enolates due to polarity mismatching. Here, the authors developed an umpolung strategy for the selective synthesis of α-alkoxy carbonyl compounds by reaction of iridium enolates with nucleophilic alcohols promoted by an iodine(III) reagent.

    • Amparo Sanz-Marco
    • , Samuel Martinez-Erro
    •  & Belén Martín-Matute

  • Article
    | Open Access

    Strong coupling of molecular vibrations to an optical cavity may catalyze thermally activated reactions, showcasing the potential of polariton chemistry. Here, the authors provide a theoretical framework explaining the chemical kinetics deriving from transit through polaritonic and dark states.

    • Jorge A. Campos-Gonzalez-Angulo
    • , Raphael F. Ribeiro
    •  & Joel Yuen-Zhou

  • Article
    | Open Access

    α-Fluoromethyl arenes are common substructures in pharmaceuticals and agrochemicals but synthetic routes are still rare. Here the authors describe Pd-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids affording structurally diverse α-fluorinated diarylmethanes.

    • Masakazu Nambo
    • , Jacky C.-H. Yim
    •  & Cathleen M. Crudden

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