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| Open AccessDehydroxylative radical N-glycosylation of heterocycles with 1-hydroxycarbohydrates enabled by copper metallaphotoredox catalysis
N-Glycosylated heterocycles play important roles in biological systems and drug development, but the synthesis heavily relies on ionic N-glycosylation. Herein, the authors report a dehydroxylative radical method for synthesizing N-glycosides by leveraging copper metallaphotoredox catalysis.
- Da-Peng Liu
- , Xiao-Sen Zhang
- & Xiang-Guo Hu
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Article
| Open AccessIterative SuFEx approach for sequence-regulated oligosulfates and its extension to periodic copolymers
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
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Article
| Open AccessPalladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes
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
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Article
| Open AccessNoncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation
Exploitation of noncovalent interactions has received much attention for the design of metal catalysts. However, because of the weak nature, CH-π interactions have been less utilized for the control of organic reactions. Here, the authors report that the CH-π interaction can be used to kinetically accelerate catalytic C-H activation of arenes.
- Yushu Jin
- , Boobalan Ramadoss
- & Laurean Ilies
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Article
| Open AccessOrganocatalytic desymmetrization provides access to planar chiral [2.2]paracyclophanes
Planar chiral [2.2]paracyclophanes have a wide range of applications in asymmetric synthesis and materials science. However, they are accessed via time-consuming chiral separations or kinetic resolution approaches. Here, the authors report a simple, metal-free protocol for organocatalytic desymmetrization of prochiral diformyl[2.2]paracyclophanes.
- Vojtěch Dočekal
- , Filip Koucký
- & Jan Veselý
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Article
| Open AccessCarbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes
Bis(N-heterocyclic carbene)-borylene complexes are capable of capturing and functionalizing CO2, but stable single-site-boron-carbon dioxide adducts are rarely reported. Here, the authors report the synthesis of a stable borylene-CO2 complex as well as the functionalization of the captured CO2.
- Jun Fan
- , An-Ping Koh
- & Cheuk-Wai So
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Article
| Open AccessPaired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst
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
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Article
| Open AccessNickel-catalyzed switchable arylative/endo-cyclization of 1,6-enynes
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
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Article
| Open AccessUmpolung reactivity of strained C–C σ-bonds without transition-metal catalysis
Umpolung reactions typically focus on carbonyls or imine derivatives. Here, the authors report the umpolung reaction of C–C σ-bonds in bicyclo[1.1.0]butanes (BCBs) with electrophilic alkenes, yielding various cyclobutenes or conjugated dienes.
- Dachang Bai
- , Xiuli Guo
- & Junbiao Chang
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Article
| Open AccessTrialkoxysilane-Induced Iridium-Catalyzed para-Selective C–H Bond Borylation of Arenes
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
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Article
| Open AccessElectroreduction of unactivated alkenes using water as hydrogen source
The reduction of unactivated alkyl alkenes is a difficult challenge in organic chemistry. Here, the authors present a silicon-mediated electroreduction of alkyl alkenes, using water as a hydrogen source, enabled by [Fe]-H.
- Yanwei Wang
- , Qian Wang
- & Youai Qiu
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Article
| Open AccessNi-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides
The direct reductive coupling of alkyl alcohol and aryl halide enables efficient access to valuable compounds, but the asymmetric pattern remains unknown. Here the authors describe the enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohol and aryl bromide in the presence of an NHC activating agent.
- Li-Li Zhang
- , Yu-Zhong Gao
- & Ze-Peng Yang
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Article
| Open AccessMetal free cross-dehydrogenative N-N coupling of primary amides with Lewis basic amines
While the homo N-N coupling of two NH moieties to form the hydrazide N-N bond is well developed, the crossdehydrogenative hetero N-N coupling remains unevolved. Here the authors present an efficient, PhI(OAc)2-mediated intermolecular N-N cross-coupling of primary benzamides with primary and secondary amines.
- Subban Kathiravan
- , Prakriti Dhillon
- & Ian A. Nicholls
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Article
| Open AccessEfficient palladium-catalyzed electrocarboxylation enables late-stage carbon isotope labelling
Carbon isotope labelling of bioactive molecules is essential for accessing the pharmacokinetic and pharmacodynamic properties of new drug entities. Here, the authors propose an electrochemical isotope-labelling protocol which enables the use of near-stoichiometric 14CO2, facilitating late-stage and single-step carbon-14 labelling of pharmaceuticals and representative precursors.
- Gabriel M. F. Batista
- , Ruth Ebenbauer
- & Troels Skrydstrup
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Article
| Open AccessReduction of Li+ within a borate anion
Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals.
- Haokun Li
- , Jiachen Yao
- & Zhenpin Lu
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Article
| Open AccessA concise and scalable chemoenzymatic synthesis of prostaglandins
Prostaglandins are of interest to synthetic chemists due to their biological activities. Here, the authors present a concise chemoenzymatic synthesis method for several representative prostaglandins, achieved in 5 to 7 steps, via the common intermediate bromohydrin, a radical equivalent of Corey lactone.
- Yunpeng Yin
- , Jinxin Wang
- & Jian Li
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Article
| Open AccessAsymmetric synthesis of P-stereogenic phosphindane oxides via kinetic resolution and their biological activity
P-stereogenic heterocycles are privileged chiral ligands and bioactive compounds, but the catalytic asymmetric synthesis of P-stereogenic phosphindane derivatives is challenging. Here, the authors report a catalytic kinetic resolution of phosphindole oxides via rhodium-catalyzed diastereo- and enantioselective conjugate addition to access enantiopure Pstereogenic phosphindane and phosphindole derivatives.
- Long Yin
- , Jiajia Li
- & Dong Guo
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Article
| Open AccessLate-stage guanine C8–H alkylation of nucleosides, nucleotides, and oligonucleotides via photo-mediated Minisci reaction
Chemically modified nucleobases and oligonucleotides are essential in several fields but introducing functional groups into nucleobases requires laborious chemical synthesis. Here, the authors report site-selective alkylation at the C8-position of guanines in guanosine, GMP, GDP, and GTP, as well as late-stage alkylation of RNA/DNA oligonucleotides through photomediated Minisci reaction.
- Ruoqian Xie
- , Wanlu Li
- & Gang Chen
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Article
| Open AccessPhoto-induced intramolecular dearomative [5 + 4] cycloaddition of arenes for the construction of highly strained medium-sized-rings
Medium-sized-ring compounds are challenging synthetic targets in organic chemistry. Here the authors report an intramolecular dearomative [5 + 4] cycloaddition of naphthalene-derived vinylcyclopropanes to construct these molecules under visible-light irradiation and a proper triplet photosensitizer.
- Min Zhu
- , Yuan-Jun Gao
- & Shu-Li You
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Article
| Open AccessSynthesis of meta-carbonyl phenols and anilines
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
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Article
| Open AccessN-Heterocyclic carbene-catalyzed enantioselective synthesis of planar-chiral cyclophanes via dynamic kinetic resolution
Planar-chiral cyclophanes are important for drug discovery but the enantioselective synthesis of planar-chiral cyclophanes remains challenging. Here the authors describe an N-heterocyclic carbene-catalyzed asymmetric construction of planar-chiral cyclophanes.
- Jiayan Li
- , Ziyang Dong
- & Changgui Zhao
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Article
| Open AccessValence-isomer selective cycloaddition reaction of cycloheptatrienes-norcaradienes
Combining data science and organic synthesis to achieve the rapid and precise creation of complex molecules while controlling multiple selectivities is an emerging trend, but few successful examples are reported. Here, the authors develop an artificial neural network regression model using bond orbital data to predict chemical reactivities.
- Shingo Harada
- , Hiroki Takenaka
- & Tetsuhiro Nemoto
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Article
| Open AccessCharacterization of elusive rhamnosyl dioxanium ions and their application in complex oligosaccharide synthesis
Characterizing highly-reactive glycosyl cation intermediates and understanding their glycosylation mechanisms are essential to the stereoselective synthesis of complex carbohydrates. Here the authors report a workflow that is utilized to characterize rhamnosyl 1,3-bridged dioxanium ions derived from C-3 p-anisoyl esterified donors.
- Peter H. Moons
- , Floor ter Braak
- & Thomas J. Boltje
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Article
| Open AccessCobalt catalyzed practical hydroboration of terminal alkynes with time-dependent stereoselectivity
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
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Article
| Open AccessEnantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution
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
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Article
| Open AccessIdentification of a potent palladium-aryldiphosphine catalytic system for high-performance carbonylation of alkenes
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
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Article
| Open AccessSilver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
Epoxides are prominent small-ring O-heterocycles found in a variety of bioactive natural products and pharmaceuticals. Here, the authors report a silver carbene strategy to achieve O-to-C atom exchange of epoxides in a single step, affording diverse fluoroalkylcyclopropanes.
- Linxuan Li
- , Paramasivam Sivaguru
- & Xihe Bi
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Article
| Open AccessOn-surface cyclization of vinyl groups on poly-para-phenylene involving an unusual pentagon to hexagon transformation
On-surface synthesis relies on carefully designed molecular precursors that are thermally activated to afford desired, covalently coupled architectures. Here, the authors study the intramolecular reactions of vinyl groups in a poly-para-phenylene-based model system and provide a comprehensive description of the reaction steps taking place on the Au(111) surface under ultrahigh vacuum conditions.
- Marco Di Giovannantonio
- , Zijie Qiu
- & Roman Fasel
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Article
| Open AccessDimethyl sulfate and diisopropyl sulfate as practical and versatile O-sulfation reagents
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
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Article
| Open AccessGeneral alkyl fluoride functionalization via short-lived carbocation-organozincate ion pairs
Many alkyl fluorides are readily available, but the synthetic applications trail behind the widely accepted utility of other halides. Here, the authors report a practical Csp3-F bond functionalization method that expands the currently restricted synthetic space of unactivated C(sp3)-F bonds, but also uses benzylic, propargylic and acyl fluorides.
- D. Lucas Kane
- , Bryan C. Figula
- & Christian Wolf
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Article
| Open AccessDioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation
The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.
- Jialiang Wei
- , Junhong Meng
- & Ning Jiao
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Article
| Open AccessZirconium and hafnium catalyzed C–C single bond hydroboration
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
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Article
| Open AccessNickel-catalyzed electrophiles-controlled enantioselective reductive arylative cyclization and enantiospecific reductive alkylative cyclization of 1,6-enynes
Transition metal-catalyzed asymmetric cyclization of 1,6-enynes is a powerful tool for the construction of chiral nitrogen-containing heterocycles, but limiting to the use of aryl or alkenyl metal reagents. Here, the authors report Ni-catalyzed enantioselective anti-arylative cyclization and enantiospecific cis-alkylative cyclization of 1,6-enynes.
- Wenfeng Liu
- , Yunxin Xing
- & Kun Shen
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Article
| Open AccessRemote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins
The synthesis of highly substituted olefins has been pursued for decades. Here, the authors show a carbonyl-directed sequential Heck/isomerization/C–H arylation of alkenes for modular synthesis of stereodefined all-carbon tetrasubstituted olefins.
- Runze Luan
- , Ping Lin
- & Weiping Su
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Article
| Open AccessCooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline
The oxidative intermolecular amination of C-H bonds represents a straightforward method to construct aliphatic allylic amines. However, the utilization of widely available internal alkenes remains a synthetic challenge. Here, the authors present a regioselective Cu-catalyzed oxidative allylic C-H amination of internal olefins with azodiformates.
- Le Wang
- , Cheng-Long Wang
- & Shu-Yu Zhang
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Article
| Open AccessMetal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes
Enhancing the sp3-hybridized character of molecular structures in drug discovery is paramount. Here, the authors introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation.
- Stefano Bonciolini
- , Antonio Pulcinella
- & Timothy Noël
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Article
| Open AccessIron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay
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
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Review Article
| Open AccessChallenges and recent advancements in the synthesis of α,α-disubstituted α-amino acids
α,α-Disubstituted α-amino acids (α-AAs) have improved properties compared to other amino acids. Here, the authors provide an overview of the recent advancements since 2015 and discuss existing challenges for their synthesis.
- Yu Zhang
- , Jaro Vanderghinste
- & Shoubhik Das
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Article
| Open AccessAccessing ladder-shape azetidine-fused indoline pentacycles through intermolecular regiodivergent aza-Paternò–Büchi reactions
Conformationally rigid 3D molecules are of high interest. Here the authors develop intermolecular aza-Paternò-Büchi reactions to access ladder-shape azetidine-fused indoline pentacycles with excellent regiodivergency and stereoselectivity.
- Jianjian Huang
- , Tai-Ping Zhou
- & Fangrui Zhong
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Article
| Open AccessCharacterization of A π–π stacking cocrystal of 4-nitrophthalonitrile directed toward application in photocatalysis
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
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Article
| Open AccessCross-catenation between position-isomeric metallacages
The study of cross-catenated metallacages could provide facile insights into achieving more precise control over low-symmetry/high-complexity hierarchical assembly systems but is currently lacking. Here, the authors report a cross-catenane formed between two position-isomeric Pt(II) metallacages in the solid state.
- Yiliang Wang
- , Taotao Liu
- & Jun Li
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Article
| Open AccessCarbene organic catalytic planar enantioselective macrolactonization
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
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Article
| Open AccessCollective total synthesis of stereoisomeric yohimbine alkaloids
Nature generates the stereoisomeric yohimbine alkaloids using bioavailable monoterpene secolaganin as the building block. Here, the authors reset the stage by the development of a bioinspired coupling, in which the pentacyclic skeleton is constructed through enantioselective kinetic resolution of an achiral, easily accessible synthetic surrogate.
- Meiyi Tang
- , Haigen Lu
- & Liansuo Zu
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Article
| Open AccessMechanochemical synthesis of organoselenium compounds
While the reported methods for the synthesis of organoselenium compounds mainly employ preformed activated selenium reagents, the direct utilization of elemental selenium in the synthesis is a more attractive but challenging strategy. Here, the authors report the rapid synthesis of versatile organoselenium compounds via mechanical stimulation.
- Shanshan Chen
- , Chunying Fan
- & Xiaofeng Wei
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Article
| Open AccessC-SuFEx linkage of sulfonimidoyl fluorides and organotrifluoroborates
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
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Article
| Open AccessEnantioselective synthesis of [4]helicenes by organocatalyzed intermolecular C-H amination
Current methods to construct helical chiral molecules for asymmetric catalysis almost entirely rely on catalytic enantiocontrolled fused-ring system extension. Herein, the authors report a direct terminal peri-functionalization strategy, which allows for efficient assembling of substituted carbohelicenes via an organocatalyzed enantioselective amination reaction.
- Xihong Liu
- , Boyan Zhu
- & Rui Wang
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Article
| Open AccessElectrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides
Open-shell catalytically active species are widely used in energy-consuming redox reactions, but their excited-state lifetimes are usually short. Here, the authors report a closed-shell thioxanthone-hydrogen anion species generated under electrochemical conditions, which can be photochemically converted to a potent and long-lived reductant.
- Wen-Jie Kang
- , Yanbin Zhang
- & Hao Guo
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Article
| Open AccessUnified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation
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
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Article
| Open AccessOrganocatalytic diastereo- and atroposelective construction of N–N axially chiral pyrroles and indoles
N–N axially chiral motifs are of synthetic interest due to their presence in natural products, pharmaceuticals, and chiral ligands. Here, the authors develop a direct catalytic synthesis of N–N atropisomers with simultaneous creation of contiguous axial and central chirality by oxidative NHC catalyzed (3 + 3) cycloaddition.
- Shao-Jie Wang
- , Xia Wang
- & Shenci Lu