Homogeneous catalysis articles within Nature Communications

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  • Article
    | Open Access

    Biaryl compounds with an axial chirality are valuable architectures but few methods have been developed for the construction of bridged biaryls, a subclass of these compounds that bear a tether to connect the two arenes and form a medium-sized ring. Here, the authors design a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization sequence of prochiral phenols for the enantioselective synthesis of biaxial bridged m-terphenyls embedded in an azocane.

    • Shuang-Hu Wang
    • , Shi-Qiang Wei
    •  & Tong-Mei Ding

  • Article
    | Open Access

    Transition-metal catalyzed cross-electrophile coupling (XEC) is a powerful tool for the construction of molecules but XEC between carbon electrophile and chlorosilanes to access organosilicon compounds remains underdeveloped. Here the authors disclose a highly efficient cobalt-catalyzed cross-electrophile alkynylation of a broad range of unactivated chlorosilanes with alkynyl sulfides as a stable and practical alkynyl electrophiles.

    • Donghui Xing
    • , Jinlin Liu
    •  & Liangbin Huang

  • Article
    | Open Access

    The noncovalent interaction of ammonium ion with multidentate oxygen-based host serving as a key reacting center in catalytic reactions is rare. In this work, the authors report a noncovalent interaction of ammonium ion enabled reactivity enhancement process, achieving the C–H functionalization of polyethylene glycols with acrylates.

    • Zongnan Zhang
    • , Xueli Lv
    •  & Rong Zeng

  • Article
    | Open Access

    Natural stilbenes show significant potential in the prevention and treatment of diseases due to their diverse pharmacological activities. Here the authors present a mild and effective Ti-catalyzed intermolecular radical-relay cycloaddition reaction with good regio- and trans-selectivity offering rapid access to structurally diverse stilbene bioisosteres.

    • Yonghong Liu
    • , Zhixian Wu
    •  & Lei Shi

  • Article
    | Open Access

    The enantioselective synthesis of S-stereogenic sulfinamides has garnered considerable attention due to their unique structural and physicochemical properties but catalytic asymmetric synthesis of sulfinamides still remains challenging. Here, the authors present the synthesis of S-stereogenic sulfinamides through the peptide-mimic phosphonium salt-catalyzed asymmetric skeletal reorganization of simple prochiral and racemic sulfoximines.

    • Zanjiao Liu
    • , Siqiang Fang
    •  & Tianli Wang

  • Article
    | Open Access

    Dearomative hydroboration of predominantly existing indole derivatives provides a straightforward strategy to synthesize boryl indolines, but developing eco-friendly methods for remains challenging. Here, the authors develop a method for heterogeneous photocatalytic trans-hydroboration of indole derivatives with NHC-borane.

    • Qiao Zhang
    • , Wengang Xu
    •  & Mingbo Wu

  • Article
    | Open Access

    In recent years a growing demand for drug design approaches that incorporate a higher number of sp3-hybridized carbons fuelled the development of innovative cross-coupling strategies to reliably introduce aliphatic fragments. Here, the authors present a powerful approach for the light-mediated B-alkyl Suzuki−Miyaura crosscoupling between alkyl boranes and aryl bromides.

    • Ting Wan
    • , Luca Capaldo
    •  & Timothy Noël

  • Article
    | Open Access

    Knowledge about the full reaction signature, such as the complete profile of products and side-products is important in accelerating discovery chemistry. Here, the authors report a methodology using high-throughput experimentation and multivariate data analysis to examine Palladium- catalyzed cross-coulpling reactions.

    • George E. Clarke
    • , James D. Firth
    •  & Ian J. S. Fairlamb

  • Article
    | Open Access

    Compared to well-developed catalytic 1,2-diazidation of alkenes, the corresponding catalytic 1,1-diazidation of alkenes has not been realized. Here, the authors report an efficient approach for catalytic 1,1-diazidation of alkenes by redox-active selenium catalysis.

    • Wangzhen Qiu
    • , Lihao Liao
    •  & Xiaodan Zhao

  • Article
    | Open Access

    A highly efficient stereoselective C−H alkylation of indoles with aryl alkenes is achieved by sustainable iron catalysis, leading to atropoenriched and enantioenriched substituted indoles with high structural diversity. Detailed mechanistic studies by experiment, Mössbauer spectroscopy and computation reveal the origin of the catalytic efficacy and stereoselectivity.

    • Zi-Jing Zhang
    • , Nicolas Jacob
    •  & Lutz Ackermann

  • Article
    | Open Access

    Installation of small aliphatic motifs within pharmaceuticals provides a medicinally relevant tool in drug discovery programmes. Here, the authors report a late-stage meta-C–H alkylation method facilitating the biological properties modulation of therapeutic agents.

    • Lucas Guillemard
    • , Lutz Ackermann
    •  & Magnus J. Johansson

  • Article
    | Open Access

    Cross-dehydrogenative coupling (CDC) of C-H bonds is an ideal approach for C-C bond construction but suffers from low selectivity of similar C-H bonds. Here, the authors describe a highly selective paired electrocatalysis strategy towards CDC combining hydrogen evolution reaction catalysis with hydride transfer catalysis.

    • Ke Liu
    • , Mengna Lei
    •  & Sheng Zhang

  • Article
    | Open Access

    Controlling regioselectivity is one of the most challenging aspects for the construction of aryl boron compounds, and there are few practical and general strategies for such transformations. Here, the authors report an iridium-catalyzed trialkoxysilane protecting group-assisted regioselective C–H borylation with various aromatic compounds.

    • Guodong Ju
    • , Zhibin Huang
    •  & Yingsheng Zhao

  • Article
    | Open Access

    Stereodefined vinylboron compounds are important organic synthons, but the selective generation of the thermodynamically unfavorable Z-isomers remains challenging. Here, the authors develop a cobalt catalytic system, enabling the transformation of terminal alkynes with excellent Z-selectivity, even in the presence of bulky substituents.

    • Jinglan Wen
    • , Yahao Huang
    •  & Peng Hu

  • 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

    The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Here, the authors develop an aryldiphosphine ligand, used in palladium-catalyzed regioselective carbonylation of alkenes, exhibiting high catalytic performance and strong oxygen-resistance stability.

    • Kang Zhao
    • , Hongli Wang
    •  & Feng Shi

  • Article
    | Open Access

    Selective cleavage and subsequent functionalization of C−C single bonds present a fundamental challenge, and the use of inexpensive and Earth-abundant group IV metals for catalytic C−C single-bond cleavage is largely underdeveloped. Here, the authors report zirconium-catalyzed C−C single-bond cleavage and subsequent hydroboration reactions.

    • Sida Li
    • , Haijun Jiao
    •  & Lipeng Wu

  • Article
    | Open Access

    Stoichiometric amounts of metal reductant and the requirement of a directing group limit the application of transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides. Here, the authors report a reductive difunctionalization of alkenes via a radical-anion relay with Na2S2O4 as both reductant and sulfone-source.

    • Xiaoya Hou
    • , Hongchi Liu
    •  & Hanmin Huang

  • Article
    | Open Access

    Photoexcitation of the electron-donor-acceptor (EDA) complexes are an effective approach to achieve radicals by triggering electron transfer but the catalytic version of EDA complex photoactivation remains underdeveloped. Here, the authors introduce 4-nitrophthalonitrile as an electron acceptor to facilitate π-stacking with electron-rich aromatics to form EDA complexes.

    • Ting Xue
    • , Cheng Ma
    •  & Rong Zeng

  • Article
    | Open Access

    Macrolactones exhibit distinct conformational and configurational properties and are widely found in natural products but catalysts to govern both macrolactone formation and stereochemical control remain largely unexplored. Here, the authors disclose an N-heterocyclic carbene (NHC)-catalyzed enantioselective synthesis of chiral macrolactones varying in ring size from sixteen to twenty members that feature distinct configurationally stable planar stereogenicity.

    • Xiaokang Lv
    • , Fen Su
    •  & Yonggui Robin Chi

  • Article
    | Open Access

    Efforts to produce aromatic monomers through catalytic lignin depolymerization were focused on aryl–ether bond cleavage, while the carbon–carbon bonds of a large fraction of aromatic monomers in lignin are difficult to cleave. Here, the authors report a catalytic autoxidation method using manganese and zirconium salts as catalysts to cleave the C–C bonds in lignin-derived dimers and oligomers from pine and poplar.

    • Chad T. Palumbo
    • , Nina X. Gu
    •  & Gregg T. Beckham

  • Article
    | Open Access

    Exploration of molybdenum complexes as homogeneous hydrogenation catalysts has garnered significant attention, but hydrogenation of unactivated olefins under mild conditions are scarce. Here, the authors report the synthesis of a cationic Mo(II) complex, which exhibits intriguing reactivity toward C2H2 and H2 under ambient pressure.

    • Minghui Xue
    • , Zhiqiang Peng
    •  & Wenguang Wang

  • 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

    Chemical recycling of plastic wastes is of great significance for sustainable development, which also represents challenges and opportunities for synthesis of value-added chemicals. Here, the authors report a general strategy to degrade polyesters via directly breaking the C-O bond by nucleophilic substitution of halide anion of ionic liquids.

    • Wei Zeng
    • , Yanfei Zhao
    •  & Zhimin Liu

  • Article
    | Open Access

    Selective defluorinative functionalization is a synthetic route to pharmaceutically important fluorine-containing compounds but activation of inert C–F bonds remains challenging. Here the authors report activation of di-or trifluoromethylated arenes for radical C–N coupling with carbazoles and aromatic amines using photoexcited copper catalysis.

    • Jun Huang
    • , Qi Gao
    •  & Jin Xie

  • Article
    | Open Access

    The simultaneous control of regio-, diastereo-, and enantioselectivity poses a significant synthetic challenge in contemporary organic synthesis. Here, the authors describe a stereodivergent allylation of 2-acylimidazoles using nickel and iridium catalysts to provide completely isomeric allylated compounds.

    • Ruimin Lu
    • , Qinglin Zhang
    •  & Chang Guo

  • Article
    | Open Access

    Stereoselective carbon-carbon bond formation via palladium-catalyzed asymmetric allylic alkylation is important to access chiral natural products but commonly used catalyst systems often require high loadings or specific preactivation protocols. Here, the authors report several chiral single-component Pd(0) precatalysts that are active at low loadings for a variety of asymmetric allylic alkylation reactions.

    • Jingjun Huang
    • , Thomas Keenan
    •  & David C. Leitch

  • 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

    While carbon-introducing difunctionalization of C-C double bonds is well established, the analogous difunctionalization for introducing germanium group and other functionalities remains elusive. Here, the authors describe a nickel-catalyzed germylative alkylation of activated olefins with easily accessible primary, secondary and tertiary alkyl bromides and chlorogermanes as the electrophiles to form C-Ge and C-Calkyl bonds simultaneously.

    • Rui Gu
    • , Xiujuan Feng
    •  & Xuan Zhang

  • Article
    | Open Access

    Low-valent nickel(0) complexes that promote α-functionalization of carbonyls leveraging its pro-nucleophilic character in conjunction with olefin acceptors are very scarce despite their attractivity. Here, the authors report a Ni(0)NHC catalyst which converts ketones and non-conjugated dienes to synthetically highly valuable α-allylated products.

    • Yi-Xuan Cao
    • , Matthew D. Wodrich
    •  & Nicolai Cramer

  • Article
    | Open Access

    γ-Amino acids and peptides analogues are common constituents of building blocks for numerous biologically active molecules, pharmaceuticals, and natural products. Here, the authors developed a multicomponent carbonylation technology that combines readily available amides, alkenes, and the feedstock gas carbon monoxide to build γ-amino acid derivatives in a single step.

    • Le-Cheng Wang
    • , Yang Yuan
    •  & Xiao-Feng Wu

  • 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

    Traditional metallaphotocatalysis often requires two or more separate catalysts and is considered to be costly and not tolerant towards a wide substrate scope. Here the authors realize metallaphotocatalysis with a bifunctional dirhodium tetracarboxylate as single catalyst component to merge carbenoid chemistry and 1O2 chemistry.

    • Taoda Shi
    • , Tianyuan Zhang
    •  & Wenhao Hu

  • Article
    | Open Access

    The development of carbonylative reactions with CO gas under mild conditions are important in organic synthesis. Here, the authors demonstrate an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence of allene and alkylzinc reagent with 1 atm of CO.’

    • Xianqing Wu
    • , Chenglong Wang
    •  & Yifeng Chen

  • Article
    | Open Access

    Remote meta selective C–H Functionalization of aromatic compounds remains challenging in chemical synthesis. Here, the authors report an iridium catalyst bearing a bidentate pyridine-pyridone ligand framework that efficiently catalyzes this meta selective borylation reaction.

    • Saikat Guria
    • , Mirja Md Mahamudul Hassan
    •  & Buddhadeb Chattopadhyay

  • Article
    | Open Access

    An efficient CO2-to-CO conversion can provide a perfect leeway for transforming waste CO2 into industrially viable CO. Here, the authors report a bio-inspired copper based synthetic catalyst that can convert CO2 to CO with minimal energy penalty in both organic and aqueous media.

    • Somnath Guria
    • , Dependu Dolui
    •  & Arnab Dutta

  • 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

    Sp2 carbon nucleophiles are generally not considered for transition metal-catalyzed asymmetric hydrofunctionalizations of unsaturated bonds due to challenges in cleaving corresponding inert sp2 C-H bonds. Here, the authors report a protocol to achieve asymmetric formal sp2 hydrocarbonations, including hydroalkenylation, hydroallenylation and hydroketenimination of both 1,3-dienes and alkynes via hydroalkylation and Wittig reaction cascade

    • Ming-Qiao Tang
    • , Zi-Jiang Yang
    •  & Zhi-Tao He

  • Article
    | Open Access

    Classical metalation reactions in organic synthesis typically involve metal-halogen exchange. Here, the authors introduce a metal-carbon exchange strategy that enables the skeletal editing of biologically relevant lactams by a Ni(0) compound.

    • Hongyu Zhong
    • , Dominic T. Egger
    •  & Bill Morandi

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