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Catalytic asymmetric synthesis of planar-chiral dianthranilides via (Dynamic) kinetic resolution
Chirality has long fascinated chemists, but asymmetric synthesis has largely focused on central, axial, and helical chirality to date. Here, the authors synthesize dianthranilides with planar chirality, via cinchona alkaloid-catalyzed (dynamic) kinetic resolution.
- Chun-Yan Guan
- , Shuai Zou
- & Guang-Jian Mei
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Article
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Enantioselective nickel-catalyzed anodic oxidative dienylation and allylation reactions
Precision control of stereochemistry in radical reactions remains a formidable challenge. Here the authors demonstrate an electricity driven asymmetric Lewis acid catalysis to facilitate asymmetric dienylation and allylation reactions, resulting in the formation of all-carbon quaternary stereocenters.
- Qinglin Zhang
- , Jiayin Zhang
- & Chang Guo
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Article
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Decarboxylative stereoretentive C–N coupling by harnessing aminating reagent
Accessing chiral alkylamines is highly important due to their ubiquity in bioactive molecules. Here, the authors present the development of stereoretentive decarboxylative amidation of carboxylic acids using dioxazolone under ambient conditions.
- Jeonguk Kweon
- , Bumsu Park
- & Sukbok Chang
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Article
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Stereospecific syn-dihalogenations and regiodivergent syn-interhalogenation of alkenes via vicinal double electrophilic activation strategy
Restricted reaction mechanism of anti-dihalogenation of alkenes makes it challenging to alter the diastereochemical course into the complementary syn-dihalogenation process. Here, the authors report a conceptually distinctive strategy for the simultaneous double electrophilic activation of the two alkene carbons from the same side to realize syn-dihalogenation.
- Hyeon Moon
- , Jungi Jung
- & Won-jin Chung
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Article
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Diastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction
Developing an efficient method for the stereocontrolled synthesis of all stereoisomers of chiral hindered ethers is highly desirable but challenging. Here, the authors report an asymmetric cascade reaction catalyzed by a bimetallic catalytic system with control over the configuration of the stereocenters of tetra-aryl substituted ethers.
- Xiangfeng Lin
- , Xia Mu
- & Can Li
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Article
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Polarizability matters in enantio-selection
Polarizability, a property that is closely related to softness in the classic theory of Hard and Soft Acids and Bases (HSAB), has been largely overlooked in connecting with enantio-selection in the past. Here, the authors show local polarizability-based electronic effects can rationalize a wide range of stereochemical outcomes in widely-known asymmetric catalytic reactions.
- Fumin Chen
- , Yu Chen
- & Xiangyou Xing
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Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks
The stereospecific Z/E isomerization of tetrasubstituted alkenes remains underdeveloped, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Here, authors report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by the photocatalyzed Z/E isomerization.
- Jie Wang
- , Jun Gu
- & Ying He
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Article
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Ni-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
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Nickel-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
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Enantioselective 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
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Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene
Developing efficient methods for the formation and cleavage of amide species is a primary research goal, but the amide C–N bond cleavage is exceptionally challenging. Here, the authors report the development of an organocatalyst that can effectively catalyze the atroposelective ring-opening of biaryl lactams via amide C–N bond cleavage.
- Yuxing Cai
- , Yuxin Zhao
- & Yong Huang
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Article
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Chiral, air stable, and reliable Pd(0) precatalysts applicable to asymmetric allylic alkylation chemistry
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
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Catalyst control over pentavalent stereocentres
Pentavalent stereocentres encode an expanded stereochemical space, but their catalytic tractability remained unprecedented. In this report, the authors report that catalyst control over pentavalent stereocentres is feasible.
- Anton Budeev
- , Jianyang Dong
- & Christof Sparr
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Article
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Stereoselectivity control in Rh-catalyzed β-OH elimination for chiral allene formation
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
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Article
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Synthesis of dienes from pyrrolidines using skeletal modification
Saturated N-heterocyclic pyrrolidines are common in natural products and medicinal compounds, but reconstruction of their skeletal structures to access new chemical space is a challenging. Here, the authors report a skeletal modification strategy for conversion of polar cyclic pyrrolidines into nonpolar linear dienes through a N-atom removal and deconstruction process.
- Haitao Qin
- , Ting Guo
- & Hongjian Lu
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Article
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Stapling strategy for slowing helicity interconversion of α-helical peptides and isolating chiral auxiliary-free one-handed forms
In nature, α-helical peptides adopt right-handed conformations dictated by L-amino acids, but isolating one-handed α-helical peptides composed of only achiral components remains a challenge. Here, the authors achieve this by optical resolution of the corresponding racemic (quasi-)static α-helical peptide with double stapling, which effectively freezes the interconversion between the right-handed (P)- and left-handed (M)-α-helices.
- Naoki Ousaka
- , Mark J. MacLachlan
- & Shigehisa Akine
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Cobalt-catalyzed atroposelective C−H activation/annulation to access N−N axially chiral frameworks
Atropisomers are an important chiral system which are widely present in natural products but atropisomerism bearing a N−N bond remains largely underdeveloped. Here, the authors report an efficient method for the enantioselective synthesis of N−N axially chiral frameworks under mild conditions via a cobalt-catalyzed atroposelective C-H activation/annulation
- Tong Li
- , Linlin Shi
- & Jun-Long Niu
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Article
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Kinetic resolution of substituted amido[2.2]paracyclophanes via asymmetric electrophilic amination
Planar chiral [2.2]paracyclophanes have found significant applications in various research fields. Here, Yang and coworkers report an efficient kinetic resolution method for various substituted amido[2.2]paracyclophanes via asymmetric C-H amination.
- Shaoze Yu
- , Hanyang Bao
- & Xiaoyu Yang
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Catalytic asymmetric dearomatization of phenols via divergent intermolecular (3 + 2) and alkylation reactions
The catalytic asymmetric dearomatization (CADA) reaction is a powerful protocol for the assembly of three-dimensional cyclic compounds but phenols have been considered challenging substrates. Here, the authors report the chiral phosphoric acidcatalyzed divergent intermolecular CADA reactions of phenols with azoalkenes to obtain tetrahydroindolone and cyclohexadienone products in good yields with excellent ee values.
- Xiang Gao
- , Tian-Jiao Han
- & Guang-Jian Mei
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Article
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Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes
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
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NHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release
The search for efficient methods for the enantioselective synthesis of cyano-containing molecules is important but synthesis methods are often limited by the need of toxic cyano salts or reduction with hydrogen gas. Here the authors report the efficient and selective access to β-cyano carboxylic esters which can be easily converted into γ-aminobutyric acid derivatives with high optical purities.
- Qingyun Wang
- , Shuquan Wu
- & Yonggui Robin Chi
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Article
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Diversity-oriented synthesis of P-stereogenic and axially chiral monodentate biaryl phosphines enabled by C-P bond cleavage
Chiral monodentate biaryl phosphines (MOPs) have attracted intense attention as chiral ligands over the past decades. Here, the authors show diversity-oriented synthesis of structurally diverse MOPs containing both phosphorus and axial chirality.
- Liangzhi Pang
- , Zhan Huang
- & Qiankun Li
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Article
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Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes
The asymmetric inverse-electron-demand oxa-Diels–Alder reaction (IODA) between activated α,β-unsaturated carbonyl compounds with highly polarized alkenes has been reported before but acroleins or simple alkenes were so-far rarely employed as substrates. Here, the authors study the catalytic asymmetric intermolecular IODA reaction between acroleins and simple alkenes.
- Lei Zeng
- , Shihan Liu
- & Lizhu Gao
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Article
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Enantioselective synthesis of chiral quinohelicenes through sequential organocatalyzed Povarov reaction and oxidative aromatization
Heterohelicenes are of increasing importance in materials science but organocatalytic enantioselective synthesis of these molecules remains challenging. Here, the authors synthesize enantioenriched 1-(3-indol)-quino[n]helicenes through chiral phosphoric acid-catalyzed Povarov reaction followed by oxidative aromatization and explore the photochemical and electrochemical properties of these compounds.
- Chengwen Li
- , Ying-Bo Shao
- & Xin Li
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Article
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Copper-catalyzed asymmetric C(sp3)-H cyanoalkylation of glycine derivatives and peptides
Incorporating cyanoalkyl moieties into amino acids and peptides is of interest for potential imaging and therapeutic purposes. Here, the authors developed a Cu-catalyzed asymmetric cyanoalkylation of glycine derivatives for the synthesis of α-cyanoalkylate amino acids and peptide modification.
- Rupeng Qi
- , Qiao Chen
- & Zhaoqing Xu
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Article
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The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles
Coordination of benzene by a tungsten complex can minimize the formation of oligomeric aromatic products in Friedel-Crafts Arylation. Here the authors show that coordinating benzene to tungsten through two carbons (dihapto-coordination) enables a rarely observed double protonation of the bound benzene, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.
- Justin T. Weatherford-Pratt
- , Jacob A. Smith
- & W. Dean Harman
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Article
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Retention time prediction for chromatographic enantioseparation by quantile geometry-enhanced graph neural network
Chromatographic enantioseparation requires tedious trials to find proper experimental conditions. Here, the authors construct a deep learning model to predict retention times of chiral molecules and obtain the separation probability under given conditions.
- Hao Xu
- , Jinglong Lin
- & Fanyang Mo
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Article
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Ligand-enabled Ni-catalysed enantioconvergent intermolecular Alkyl-Alkyl cross-coupling between distinct Alkyl halides
Accessing saturated stereogenic centers by asymmetric alkyl-alkyl formation is attractive yet challenging. Here, the authors develop a Ni-catalysed cross-coupling reaction of two alkyl halides enabled by the in-situ formation of alkyl zinc from one alkyl halide.
- Wen-Tao Zhao
- , Jian-Xin Zhang
- & Wei Shu
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Article
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Stereoselective C–O silylation and stannylation of alkenyl acetates
Carbon-heteroatom bond formation reactions are of high interest in synthetic organic chemistry. Here, the authors report the cobalt-catalyzed synthesis of tri- and tetrasubstituted alkenyl silanes and stannanes via C–O functionalization of vinyl acetates using silylzinc pivalate and stannylzinc chloride as the nucleophiles.
- Ying Hu
- , Jiali Peng
- & Jie Li
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Article
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Interplay of diruthenium catalyst in controlling enantioselective propargylic substitution reactions with visible light-generated alkyl radicals
Construction of stereogenic carbon centers of propargylic alcohols with free radicals could mark a simple route to molecular complexity from easily obtained starting materials. Here the authors present a strategy to control enantioselective propargylic substitution reactions with alkyl radicals under photoredox conditions.
- Yulin Zhang
- , Yoshiaki Tanabe
- & Yoshiaki Nishibayashi
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Article
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Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands
The stereoselective synthesis of olefins from alkynes is a long-standing challenge in organic synthesis. Here, the authors report the chromium-catalyzed alkyne hydrogenation; E- or Z-olefins are obtained depending on the carbene ligand used.
- Liang Ling
- , Chenyang Hu
- & Xiaoming Zeng
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Article
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Dearomative triple elementalization of quinolines driven by visible light
Organoboron and organosilicon compounds have potential applications in various fields including materials science and medicinal chemistry. Here the authors report a protocol that enables the dearomative carbo-sila-boration of quinolines.
- Shiho Ishigaki
- , Yuki Nagashima
- & Ken Tanaka
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Article
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Modulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis
The selective construction of C-C double bonds in alkenes, which can be one of two isomers, is a fundamental focus of organic chemistry. Here, the authors systematically investigated the stereoselectivity in allylic C(sp3)-H bond arylations and demonstrated a ligand switch could allow a stereodivergent synthesis of silyl enol ethers.
- Long Huang
- , Marcin Szewczyk
- & Magnus Rueping
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Article
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Preferential molecular recognition of heterochiral guests within a cyclophane receptor
The design of synthetic supramolecular receptors capable of enantioselective molecular recognition is challenging. Here the authors report a perylene bisimide-based receptor that forms heterochiral host-guest complexes upon aromatic guests encapsulation; guest recognition can be modulated by peripheral substitution of the binding site.
- Manuel Weh
- , Kazutaka Shoyama
- & Frank Würthner
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Article
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Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides
Precise matching of reaction rate and electric potential of electrodes in paired electrolysis is challenging. Here, the authors develop paired-electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling of α-chloroesters and aryl bromides.
- Dong Liu
- , Zhao-Ran Liu
- & Tian-Sheng Mei
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Article
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Accessing chiral sulfones bearing quaternary carbon stereocenters via photoinduced radical sulfur dioxide insertion and Truce–Smiles rearrangement
The preparation of chiral sulfones featuring quaternary carbon stereocenters remains challenging. Here the authors report the synthesis of such compounds via a multicomponent reaction involving a photoinduced radical sulfur dioxide insertion followed by an asymmetric Truce–Smiles rearrangement.
- Jiapian Huang
- , Fei Liu
- & Jie Wu
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Article
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Asymmetric construction of allylicstereogenic carbon center featuring atrifluoromethyl group via enantioselective reductive fluoroalkylation
The efficient construction of trifluoromethylated alkanes bearing a CF3 chiral center is of great importance in organic synthesis. Here, the authors disclose the enantioselective syntheses of α-trifluoromethylated allylic alkanes via reductive trifluoroalkylation.
- Ruo-Xing Jin
- , Bing-Bing Wu
- & Xi-Sheng Wang
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Article
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Nickel-catalyzed switchable 1,3-dienylation and enantioselective allenylation of phosphine oxides
Asymmetric catalytic methods for the divergent construction of phosphoryl derivatives are not widely available. Here, the authors show nickel-catalyzed dienylation and enantioselective allenylation of phosphine oxides with high chemo-, regio-, and enantioselectivity.
- Jiayin Zhang
- , Xihao Chang
- & Chang Guo
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Article
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Enantioselective synthesis of N-alkylindoles enabled by nickel-catalyzed C-C coupling
Enantioenriched N-alkylindole compounds, in which nitrogen is bound to a stereogenic sp3 carbon, are target molecules in the fields of biological, medicinal, and organic chemistry. Here the authors show a nickel-catalyzed C-C coupling protocol to synthesize these molecules from N-indolylsubstituted alkenes.
- Lun Li
- , Jiangtao Ren
- & Deyun Qian
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Article
| Open Access
The occurrence of ansamers in the synthesis of cyclic peptides
The occurrence of isomers of the bicyclic octapeptide α-amanitin, which presents a macrolactam with a tryptathionine cross-link forming a handle, has been reported under the term of atropoisomers. Here, the authors synthesize its analogs and analyse their isomers, proposing and describing for them the term ansamer.
- Guiyang Yao
- , Simone Kosol
- & Roderich D. Süssmuth
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Article
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Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst
α-Alkylation of β-keto esters is a frequently used reaction for carbon–carbon bond formation, but a general, stereoselective version of this reaction is challenging to realize. Here, the authors report a combined ruthenium and palladium catalytic system for the asymmetric dehydrative condensation between cinnamyl-type allylic alcohols and β-keto esters.
- Thien Phuc Le
- , Shinji Tanaka
- & Masato Kitamura
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Article
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Enantioselective nickel-catalyzed dicarbofunctionalization of 3,3,3-trifluoropropene
Strategies for the catalytic asymmetric synthesis of trifluoromethylated compounds remain scarce. Here, the authors report the nickel-catalyzed enantioselective dicarbofunctionalization of 3,3,3-trifluoropropene.
- Yun-Ze Li
- , Na Rao
- & Xingang Zhang
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Article
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Collective total synthesis of C4-oxygenated securinine-type alkaloids via stereocontrolled diversifications on the piperidine core
A general synthetic solution toward high-oxidation state securinega alkaloids could be useful for systematic biological studies. Here, the authors report a divergent synthesis of C4-oxygenated securinega alkaloids via stereocontrolled diversifications on the piperidine core.
- Sangbin Park
- , Gyumin Kang
- & Sunkyu Han
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Article
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Synthesis of cis-thiiranes as diastereoselective access to epoxide congeners via 4π-electrocyclization of thiocarbonyl ylides
Thiirane, the sulfur congener of oxirane, has been hard to access in a stereodefined form. Here, the authors accomplished a highly stereoselective synthesis of cis-diarylthiiranes through the stereospecific sulfurization of E,E-aldazine N-oxides.
- Su-min Song
- , Jaeseong Jin
- & Won-jin Chung
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Article
| Open Access
Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes
Regio- and stereoselective transition-metal catalysed hydrosilylation of terminal allenes to access (E)-allylsilanes are challenging organic transformations. Herein, the authors synthesize (E)-allylsilanes via copper-catalyzed hydrosilylation of terminal allenes.
- Shaowei Chen
- , Xiaoqian He
- & Xiao Shen
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Article
| Open Access
Nickel(0)-catalyzed divergent reactions of silacyclobutanes with internal alkynes
Transition metal-catalyzed reactions of silacyclobutanes to access structurally diverse organosilicon compounds have attracted attention in recent years. Here, the authors show nickel-catalysed, ligand-controlled chemodivergent reactions of these compounds with alkynes to (benzo)silacyclohexenes and allyl vinylsilane.
- Xi-Chao Wang
- , Bo Li
- & Dongbing Zhao
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Article
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Enyne diketones as substrate in asymmetric Nazarov cyclization for construction of chiral allene cyclopentenones
Developing classes of substrates for the Nazarov reaction is an important endeavour for synthetic chemistry. Here, the authors report how enyne diketones undergo rhodium-catalyzed metal-organo relay catalysis for the enantioselective construction of chiral allene cyclopentenones via Nazarov cyclisation in good yields and enantioselectivities.
- Shengbiao Tang
- , Peng Zhang
- & Jiangtao Sun
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Article
| Open Access
Engineered non-covalent π interactions as key elements for chiral recognition
Non-covalent π interactions have been rarely used as a design element for promoting chemical reactions. Here the authors report a Sharpless asymmetric dihydroxylation (SAD)-based kinetic resolution in which a-priori-designed non-covalent forces play a central role in differentiating the enantiomeric substrates.
- Ming Yu Jin
- , Qianqian Zhen
- & Chen Xu
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Article
| Open Access
Construction of boron-stereogenic compounds via enantioselective Cu-catalyzed desymmetric B–H bond insertion reaction
Enantioselective catalytic methods for the construction of boron-stereogenic compounds are elusive. In this article, the authors describe a route to these compounds via a copper-catalysed desymmetric B-H insertion on 2-arylpyridine-boranes with carbenes.
- Guan Zhang
- , Zhihan Zhang
- & Qiuling Song
Why •CF2H is nucleophilic but •CF3 is electrophilic in reactions with heterocycles