Reaction mechanisms articles within Nature Communications

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  • Article
    | Open Access

    The control of reaction quantum efficiencies is a fundamental photochemical problem. Here the authors use comparative quantum-classical dynamics to reveal that the synchronization of specific vibrations with the reaction coordinate is a key promoting factor.

    • Alejandro Blanco-Gonzalez
    • , Madushanka Manathunga
    •  & Massimo Olivucci

  • Article
    | Open Access

    The synthesis of sequence-regulated oligosulfates has not yet been established due to the difficulties in precise reactivity control. Here, the authors report a multi-directional divergent iterative method to furnish oligosulfates based on a chain homologation approach, in which the fluorosulfate unit is regenerated.

    • Min Pyeong Kim
    • , Swatilekha Kayal
    •  & Sung You Hong

  • Article
    | Open Access

    Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial but the chirality orginiating from the distorted structure around heptagon-containing polyarenes is largely overlooked. Herein the authors present a highly enantioselective synthesis for fabrication of all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross–coupling of benzyl bromides and N-arylsulfonylhydrazones.

    • Huan Zhang
    • , Chuan-Jun Lu
    •  & Ren-Rong Liu

  • Article
    | Open Access

    Multiple autocatalytic reactions producing thiols are known, but negative feedback loop motifs are unavailable for thiol chemistry. Here, the authors develop a negative feedback loop based on the selenocarbonates, in which thiols induce the release of aromatic selenols that catalyze the oxidation of thiols by organic peroxides.

    • Xiuxiu Li
    • , Polina Fomitskaya
    •  & Sergey N. Semenov

  • Article
    | Open Access

    Divergent functionalizations of pi bonds allow for synthetic chemists to move from simplicity to complexity. Here, the authors report a nickel-catalyzed switchable arylation/cyclization of 1,6-enynes in which the nature of the ligand dictates the regioselectivity of alkyne arylation, while the electrophilic trapping reagents determine the selectivity of the cyclization mode.

    • Wenfeng Liu
    • , Wei Li
    •  & Wangqing Kong

  • Article
    | Open Access

    Phenols and anilines are of extreme importance for medicinal chemistry and material science but the selective preparation of meta-substituted phenols and anilines remains challenging. Here the authors report an efficient copper-catalyzed dehydrogenation strategy to exclusively synthesize meta-carbonyl phenols and anilines from carbonyl substituted cyclohexanes.

    • Bao-Yin Zhao
    • , Qiong Jia
    •  & Yong-Qiang Wang

  • Article
    | Open Access

    Site- and stereoselective C–H functionalization is challenging in the synthetic chemistry, and the catalytic enantioselective C(sp3)–H functionalization based on vinyl cations has scarcely explored. Here, the authors report an asymmetric copper-catalyzed tandem diyne cyclization/unactivated C(sp3)–H insertion reaction via a kinetic resolution.

    • Yang-Bo Chen
    • , Li-Gao Liu
    •  & Long-Wu Ye

  • Article
    | Open Access

    O-Sulfation is a vital post-translational modification in bioactive molecules, yet there are significant challenges for the synthesis. Here, the authors report a general and robust approach to O-sulfation by harnessing the tunable reactivity of dimethyl sulfate or diisopropyl sulfate under tetrabutylammonium bisulfate activation.

    • Shuaishuai Yue
    • , Guoping Ding
    •  & Jiakun Li

  • Article
    | Open Access

    Sulfur fluoride exchange (SuFEx), a new type of linkage reaction, has great potential for application in functional molecule linkage to prepare pharmaceuticals, biomolecules, and polymers. Herein, the authors report the synthesis of a range of sulfoximines through SuFEx reaction between sulfonimidoyl fluorides and aryl/alkyl organotrifluoroborates.

    • Suqin Zhao
    • , Daming Zeng
    •  & Xuefeng Jiang

  • Article
    | Open Access

    Direct and site-selective C–H functionalization of alkenes under environmentally benign conditions represents a useful and attractive yet challenging transformation to access value-added molecules. Here, the authors report a protocol for a variety of intermolecular Heck-type functionalization of C(sp2)–H bond of alkenes by thianthrenation.

    • Ming-Shang Liu
    • , Hai-Wu Du
    •  & Wei Shu

  • Article
    | Open Access

    All-carbon quaternary stereocenters are an important synthetic motif but are especially difficult to synthesize enantioselectively. Here, the authors demonstrate the organocatalytic regio- and enantioselective synthesis of valuable acyclic 1,4-dicarbonyl products with vinylated and arylated quaternary centers.

    • Po-Kai Peng
    • , Andrew Isho
    •  & Jeremy A. May

  • Article
    | Open Access

    Directing group strategies have been used extensively in C–H activation reactions but current methods rely heavily on coordination with nitrogen or oxygen atoms in molecules and have therefore been found to exhibit limited generality in asymmetric syntheses. Here, the authors report enantioselective C–H activation with unsaturated hydrocarbons directed by phosphorus centres to rapidly construct libraries of axially chiral phosphines through dynamic kinetic resolution.

    • Zexian Li
    • , Minyan Wang
    •  & Zhuangzhi Shi

  • Article
    | Open Access

    Here the authors demonstate that counter to expectation provided by the relevant standard reduction potentials, a chloroberyllate, [{SiNDipp}BeClLi]2, reacts with the group 1 elements (M = Na, K, Rb, Cs) to provide the respective heavier alkali metal analogues, [{SiNDipp}BeClM]2.

    • Kyle G. Pearce
    • , Han-Ying Liu
    •  & Michael S. Hill

  • Article
    | Open Access

    Prodrug photolysis enables spatiotemporal control of drug release at the desired lesions, but most of the photocleavable groups cannot be directly activated by near-infrared (NIR) light that features deep penetration and low phototoxicity. Here, the authors report an upconversion-like process via only one step of energy transfer for NIR light-triggered prodrug photolysis.

    • Kaiqi Long
    • , Wen Lv
    •  & Weiping Wang

  • Article
    | Open Access

    Fused carbocycles are key structural elements of molecules in nature and they are often found in drugs and organic materials, but bicyclic systems containing six and seven-membered rings are difficult to prepare. Here, the authors functionalize an azulene skeleton that consists of fused five and seven-membered rings and carry out a ring expansion reaction to afford the desired bicycles.

    • Sangjune Park
    • , Cheol-Eui Kim
    •  & Phil Ho Lee

  • Article
    | Open Access

    Multicomponent cross-coupling of alkenes with silicon reagents is used to yield complex silicon-containing compounds from readily accessible feedstock chemicals but the reaction with simple alkenes remains challenging. Here, the authors report a regioselective silylalkylation of simple alkenes, which is enabled by using a stable Ni(II) salt and an inexpensive trans-1,2-diaminocyclohexane ligand as a catalyst.

    • Chao Ding
    • , Yaoyu Ren
    •  & Guoyin Yin

  • Article
    | Open Access

    Recently, the asymmetric bifunctionalization of alkenes has received much attention but the development of enantioselective alkoxyalkenylation has posed a considerable challenge and has lagged largely behind. Here, the authors report a palladium-catalyzed enantioselective alkoxyalkenylation reaction, using a range of primary, secondary, and tertiary γ-hydroxyalkenes with alkenyl halides.

    • Shuai Zhu
    • , Zihao Ye
    •  & Junliang Zhang

  • Article
    | Open Access

    The chiral allene formation reactions catalyzed by palladium occur via a syn elimination mechanism, but there is a lack in understanding of the stereoselectivity in rhodium catalyzed reactions, specifically the β-OH elimination step. Here, the authors report the sterically controlled Rh-catalyzed SN2’-type substitution reactions of tertiary propargylic alcohols with arylmetallic species affording the non-readily available enantioenriched tetrasubstituted allenes via either exclusive syn- or anti-β-OH elimination.

    • Jie Wang
    • , Wei-Feng Zheng
    •  & Shengming Ma

  • Article
    | Open Access

    The formal C–C bond insertion into aldehydes is an attractive methodology for the assembly of homologated carbonyl compounds but the homologation of aldehydes has been limited to diazo approach and the enantioselective reaction was rarely developed. Here, the authors report an asymmetric formal C–C bond insertion into aldehydes through diyne cyclization strategy

    • Cui-Ting Li
    • , Lin-Jun Qi
    •  & Bo Zhou

  • Article
    | Open Access

    Alkylphosphonates are used as chargeneutral replacements for naturally-occurring phosphodiester backbones in nucleotides but the choice of alkyl moieties that can be attached to phosphorus atoms in these compounds is limited to methyl groups or primary/secondary alkyls. Here, the authors demonstrate the tertiary alkylation of the phosphorus atoms of phosphites bearing two 2’-deoxynuclosides using a carbocation generated via a light-driven radical-polar crossover mechanism

    • Kenji Ota
    • , Kazunori Nagao
    •  & Hirohisa Ohmiya

  • Article
    | Open Access

    Alkyl halides, widely recognized as important building blocks and reagents in organic synthesisbut generating alkyl radicals directly from unactivated alkyl halides under mild conditions remains a challenge. Here the authors report an effective electrooxidation strategy for generating alkyl radicals from unactivated alkyl iodides via an electrochemical halogen-atom transfer process under mild conditions

    • Xiang Sun
    •  & Ke Zheng

  • Article
    | Open Access

    Photocatalytic selective C(sp3)–H activation/cross-coupling reactions are appealing in organic synthesis. Here the authors describe the development of excited-state Pd-catalyzed dehydrogenative β-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C−S cross-coupling processes at room temperature.

    • Krishnamoorthy Muralirajan
    • , Rajesh Kancherla
    •  & Magnus Rueping

  • Article
    | Open Access

    Silicon-stereogenic optically active silylboranes could potentially allow the formation of chiral silyl nucleophiles as well as the synthesis of various chiral silicon compounds but the synthesis of such silicon-stereogenic silylboranes remains underdeveloped. Here, the authors report the synthesis of silicon-stereogenic optically active silylboranes via a stereospecific Si–H borylation of chiral hydrosilanes in high yield enantiospecificity

    • Xihong Wang
    • , Chi Feng
    •  & Hajime Ito

  • Article
    | Open Access

    The precise and efficient construction of axially chiral scaffolds, particularly toward the aryl-alkene atropoisomers remains challenging. Here, the authors discuss an organocatalytic asymmetric nucleophilic aromatic substitution reaction of aldehyde-substituted styrenes involving a dynamic kinetic resolution process via a hemiacetal intermediate, offering a pathway to axial styrene scaffolds.

    • Fengyuan Guo
    • , Siqiang Fang
    •  & Tianli Wang

  • Article
    | Open Access

    Functionalization of 1,3-enyne represent a powerful method to construct allenyl- and propargylderivatives, but hydrosilylation reaction of 1,3-enynes remains underdeveloped. Here, the authors report a copper-catalyzed ligand-controlled selective 1,2- and 1,4- hydrosilylation of 1,3-enynes which proceeds enantioselectively with high yields.

    • Zi-Lu Wang
    • , Qi Li
    •  & Yun-He Xu

  • Article
    | Open Access

    Indole alkaloids are one of the largest alkaloid classes, proving valuable structural moiety in pharmaceuticals but the direct single-step synthesis with broad structural diversity remains challenging. Herein, the authors report a modular assembly of tetrahydrocarboline type of indole alkaloids from simple building blocks in a single step while showing broad compatibility with medicinally relevant functionality

    • Jiaming Li
    • , Zhencheng Lai
    •  & Sunliang Cui

  • Article
    | Open Access

    Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Here, the authors report an on-cycle mechanism for CoCl2bpy2 catalyzed Negishi-type cross-coupling describing a full catalytic cycle for this reaction using multiple spectroscopic studies.

    • Xu Luo
    • , Dali Yang
    •  & Aiwen Lei

  • Article
    | Open Access

    Light driven synthetic molecular motors represent crucial building blocks for advanced molecular machines and their applications but the development of very fast motors remains challenging. Here the authors restrict fast molecular motor rotations and force them to proceed in two separate rotation-photoequilibria enabling them to elucidate the directionality of the motion.

    • Benjamin Lukas Regen-Pregizer
    • , Ani Ozcelik
    •  & Henry Dube

  • Article
    | Open Access

    The application of catalytic dynamic kinetic asymmetric transformation (DyKAT) in axial chirality is limited to fivemembered metalacyclic intermediate-directed equilibrium of substrate enantiomers. Here, the authors report a tetracoordinate boron-directed DyKAT of racemic, configurationally stable 3-bromo- 2,1-azaborines for the construction of C-B axial chirality.

    • Kai Yang
    • , Yanfei Mao
    •  & Qiuling Song

  • Article
    | Open Access

    Chemoselective reactions of two or multiple functional groups with similar reactivities remain an ongoing challenge in chemistry. Here the authors disclosed a chemoselective reaction of enedial and observed that the high chemoselectivity is mainly controlled via redox (rather than steric) properties of the substrate/catalyst.

    • Guodong Fan
    • , Qingyun Wang
    •  & Yonggui Robin Chi

  • Article
    | Open Access

    Allylic substitution reactions have emerged as a powerful tool for the construction of C − C/X bonds. Here, the authors develop a migratory strategy of allylic arylation under the catalysis of nickel and lanthanide triflate.

    • Dan Zhao
    • , Bing Xu
    •  & Can Zhu

  • Article
    | Open Access

    The versatility and importance of β,γ-unsaturated ketones has been appreciated for a long time in synthesis and medicinal chemistry. Here, the authors use carboxylic acids and readily available olefins as substrates for transformations involving N‑heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for the synthesis of β,γ-unsaturated ketones.

    • Xiaochen Wang
    • , Rongxin Yang
    •  & Qingmin Wang

  • Article
    | Open Access

    Electrocyclic reactions proceed through critical geometries, which are known as pericyclic transition states in thermal reactions and pericyclic minima in photochemical reactions. Here, the authors image the structure of a pericyclic minimum in real time using a combination of ultrafast electron diffraction and ab initio dynamics simulations.

    • Y. Liu
    • , D. M. Sanchez
    •  & T. J. A. Wolf

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