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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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Catalytic asymmetric [4 + 2] dearomative photocycloadditions of anthracene and its derivatives with alkenylazaarenes
While significant progress has been made in classical Diels-Alder reactions, the use of simple and inert feedstock chemicals under mild reaction conditions still remains challenging. Here the authors present the development of catalytic asymmetric [4 + 2] dearomative photocycloaddition involving anthracene and its derivatives with alkenylazaarenes.
- Dong Tian
- , Wenshuo Shi
- & Zhiyong Jiang
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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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Asymmetric C–H Dehydrogenative Alkenylation via a Photo-induced Chiral α‑Imino Radical Intermediate
The direct alkenylation with simple alkenes stands out as the most ideal yet challenging strategy for obtaining high-valued desaturated alkanes. Herein, the authors present a direct asymmetric dehydrogenative α-C(sp3)-H alkenylation of carbonyls based on synergistic photoredox-cobalt-chiral primary amine catalysis under visible light.
- Zongbin Jia
- , Liang Cheng
- & Sanzhong Luo
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Enantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch
Catalytic and enantioselective construction of chiral α,α-dialkyl indoles represents an important yet challenging objective to be developed. Herein the authors describe a cobalt catalyzed enantioselective anti-Markovnikov alkene hydroalkylation via the remote stereocontrol for the synthesis of α,α-dialkyl indoles and other N-heterocycles.
- Jiangtao Ren
- , Zheng Sun
- & Zhihui Shao
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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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Iron-catalyzed stereoselective C–H alkylation for simultaneous construction of C–N axial and C-central chirality
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
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Pathway-divergent coupling of 1,3-enynes with acrylates through cascade cobalt catalysis
The development of divergent reaction pathways controlled by different ligands is a critical goal. Here the authors describe a cobalt-catalyzed strategy for cascade coupling of 1,3-enynes with two molecules of acrylates through three reaction modes.
- Heng Wang
- , Xiaofeng Jie
- & Fanke Meng
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Article
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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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Organocatalytic 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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Asymmetric 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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N-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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Desymmetric homologating annulation to access chiral pentafulvenes and their application in bioimaging
Polycyclic/multisubstituted pentafulvenes are of interest as they frequently occur in biologically relevant motifs, electrochromic dyes, and solar cells. Here, the authors report an enantioselective homologating annulation of cyclopent-4-ene-dione with 3-cyano-4-methylcoumarins through L-tert-leucine derived thiourea catalysis, affording a wide range of enantioenriched polycyclic multi-substituted embedded aminopentafulvenes.
- Sanjay Singh
- , Ravi Saini
- & Ravi P. Singh
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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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Asymmetric α-C(sp3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis
Primary alkyl amines are highly reactive in N-nucleophilic reactions with electrophiles but their α-C–H bonds are unreactive towards electrophiles due to their extremely low acidity. Combining 8-diazafluoren-9-one with an iridium catalyst, the authors demonstrate direct asymmetric α-C-H alkylation of unprotected primary alkyl amines with allylic carbonates.
- Jianyu Li
- , Sheng Gong
- & Baoguo Zhao
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Organocatalytic 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
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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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Modular access to chiral bridged piperidine-γ-butyrolactones via catalytic asymmetric allylation/aza-Prins cyclization/lactonization sequences
N/O-Heterocycles are widely spread in natural products and drug candidates. Here, the authors report a modular access to bridged piperidine-γ-butyrolactones via Cu/Ir-catalyzed asymmetric allyation and aza-Prins cyclization/lactonization sequences.
- Cong Fu
- , Ling He
- & Chun-Jiang Wang
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Atroposelective hydroarylation of biaryl phosphines directed by phosphorus centres
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
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Catalytic stereodivergent allylic alkylation of 2-acylimidazoles for natural product synthesis
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
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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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Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
Ligands capable of accelerating and inducing enantioselectivity in C–H activations with base metal catalysts have remained elusive. Here, the authors report a ligand-accelerated enantioselective C–H alknylation, using a chiral BINOL ligand with a copper catalyst.
- Xin Kuang
- , Jian-Jun Li
- & Jin-Quan Yu
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Nickel-catalyzed direct stereoselective α-allylation of ketones with non-conjugated dienes
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
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Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water
Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is challenging. Here, the authors present, a family of amphiphilic one handed helical polyisocyanides bearing phosphine pendants which self-assembled into well-defined chiral micelles in water and show thermo-responsiveness
- Lei Xu
- , Li Zhou
- & Zong-Quan Wu
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Article
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Cu-catalyzed asymmetric regiodivergent electrosynthesis and its application in the enantioselective total synthesis of (-)-fumimycin
Quaternary amino acids are important building blocks and precursors of medicinal compounds. Here, the authors describe a copper-catalyzed regiodivergent electrochemical core structure-oriented crossdehydrogenative coupling reaction of Schiff bases and commercially available hydroquinones to obtain three classes of chiral quaternary amino acid derivatives
- Tian Xie
- , Jianming Huang
- & Chang Guo
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Ultra-high-throughput mapping of the chemical space of asymmetric catalysis enables accelerated reaction discovery
The discovery of highly enantioselective catalysts is challenging due to the complex multidimensional chemical space of asymmetric catalysis and inefficient screening methods. Here, the authors report a general strategy for ultra-high-throughput mapping of the chemical space of asymmetric catalysis with a combination of ion mobility-mass spectrometry and a diastereoisomerization strategy and identify enantioselective primary amine organocatalysts using this method.
- Wenjing Nie
- , Qiongqiong Wan
- & Suming Chen
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All-round catalytic and atroposelective strategy via dynamic kinetic resolution for N-/2-/3-arylindoles
While a variety of well-established methods enable the control of a stereogenic center, a catalytic method for controlling a stereogenic axis in one substrate is typically unavailable for controlling axial chirality in other substrates with a similar structure. Here, the authors report o-amidobiaryl as a flexible platform for chiral phosphoric acid catalyzed atroposelective dynamic kinetic resolution.
- Ahreum Kim
- , Chanhee Lee
- & Yongseok Kwon
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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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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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Photoredox cobalt-catalyzed regio-, diastereo- and enantioselective propargylation of aldehydes via propargyl radicals
Catalytic enantioselective introduction of a propargyl group is an important carbon–carbon forming reactions but only few Cu- or Ni-catalyzed protocols with limited reaction modes are known. Here, the authors describe a photoredox/cobalt-catalyzed propargyl addition to aldehydes via propargyl radicals which enables the construction of a broad scope of homopropargyl alcohols.
- Lei Wang
- , Chuiyi Lin
- & Fanke Meng
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Article
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Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis
Axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active compounds but asymmetric synthesis of N-arylpyrroles is challenging. Here, the authors develop a diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis.
- Lei Dai
- , Xueting Zhou
- & Yixin Lu
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Article
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Copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of 1,3-enynes and azomethine ylides
One of the most efficient method to access chiral poly-substituted pyrrolidines is the catalytic asymmetric 1,3-dipolar cycloaddition, but using this reaction with weakly activated alkenes remains elusive. Here, the authors disclose a copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides and 1,3-enynes.
- Bo-Ran Wang
- , Yan-Bo Li
- & Liang Yin
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Article
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Rhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles
Molecules with axial chirality are of intense focus to the synthetic organic community, but the axes most commonly explored are carbon–carbon and carbon–heteroatom. Here the authors report the syntheses of diaxially chiral biaryls containing N-N and C-N/C-C axes, achieved via rhodium catalysis.
- Yishou Wang
- , Xiaohan Zhu
- & Xingwei 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
| Open Access
Data-driven design of new chiral carboxylic acid for construction of indoles with C-central and C–N axial chirality via cobalt catalysis
The design of efficient and selective catalysts is a formidable challenge in chemical science. Here the authors design a data-driven workflow to achieve the digitalized knowledge transfer between the synthetically relevant transformations, which was demonstrated in the prediction of chiral carboxylic acid co-catalyst for the cobalt-catalyzed asymmetric C–H alkylation of indoles.
- Zi-Jing Zhang
- , Shu-Wen Li
- & Lutz Ackermann
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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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Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis
Enantioselective α-allylic allenylation of carbonyls is a straightforward approach to access chiral allenes that are of significant relevance as synthons and bio-active products. Here, the Luo group describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes, via a combined chiral primary amine and palladium catalyst system.
- Chang You
- , Mingying Shi
- & Sanzhong Luo
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Article
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Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides
Metal reductants show low efficiency in enantioselective nickel-catalyzed reductive cross-coupling of aryl aziridines with aryl iodides. Here, the authors improve the reaction efficiency through an electrochemical method.
- Yun-Zhao Wang
- , Zhen-Hua Wang
- & Tian-Sheng Mei
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Article
| Open Access
Design of C1-symmetric tridentate ligands for enantioselective dearomative [3 + 2] annulation of indoles with aminocyclopropanes
Polycyclic indolines are valuable skeletons in drug discovery. Here, the authors report an asymmetric dearomative [3 + 2] annulation of indoles with aminocyclopropanes to construct tricyclic indolines.
- Hai-Xia Wang
- , Chun Yang
- & Hai-Ming Guo
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Article
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Asymmetric hydrogenation of 1,1-diarylethylenes and benzophenones through a relay strategy
Distinguishing the prochiral faces of a double bond can be challenging for hydrogenation catalysts. Here, authors show a relay strategy for constructing compounds with a chiral gem-diaryl carbon center via selective arene exchange between 1,1-diarylethylenes or benzophenones with (naphthalene)Cr(CO)3 and subsequent asymmetric hydrogenation.
- Ke Li
- , Wen-Qiang Wu
- & Hang Shi
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Article
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Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry
1,6 enynes are a useful synthetic building block, but their use asymmetric intramolecular reductive couplings with cobalt catalysts have not been well-explored. Here, the authors describe an enantioselective intramolecular reductive coupling of enynes via the combination of electrochemistry and cobalt catalysis.
- Shiquan Gao
- , Chen Wang
- & Junliang Zhang
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Article
| Open Access
Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization
Asymmetric ring-opening (ARO) reactions, which can help quickly build molecular complexity, have not been extensively shown via β-oxygen elimination. Here, the authors report a cobalt(III)-catalyzed ARO reaction, providing mechanistic insights and the origins of the diastereo- and enantioselectivity.
- Yang Zheng
- , Wen-Yun Zhang
- & Shu-Li You
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Article
| Open Access
Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis
Chiral α-acylated N-heterocycles are commonly found in pharmaceutical drugs, natural products, and catalysts for asymmetric synthesis. Here, the authors describe a cooperative nickel/photoredox catalysis strategy for the site- and enantioselective cross-coupling of saturated azacycles and carboxylic acids to access such valuable heterocyclic molecules.
- Xiaomin Shu
- , De Zhong
- & Haohua Huo
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Article
| Open Access
Stereodivergent synthesis of chiral succinimides via Rh-catalyzed asymmetric transfer hydrogenation
Chiral succinimides are ubiquitous in bioactive compounds. Here, authors report a stereodivergent method for accessing 3,4-disubstituted succinimides, and the origin of stereoselectivity is elucidated by experimental and theoretical investigations.
- Fangyuan Wang
- , Zongpeng Zhang
- & Xumu Zhang
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Article
| Open Access
Chiral aldehyde-nickel dual catalysis enables asymmetric α−propargylation of amino acids and stereodivergent synthesis of NP25302
The combination of transition metal catalysis and organocatalysis can afford both good reactivity and selectivity. Here, the authors present an α − propargylation of N-unprotected amino acid esters with propargylic alcohol derivatives via dual nickel and chiral aldehyde catalysis.
- Fang Zhu
- , Chao-Xing Li
- & Qi-Xiang Guo
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Article
| Open Access
Enantioselective Ugi and Ugi-azide reactions catalyzed by anionic stereogenic-at-cobalt(III) complexes
Ugi reactions are well known multicomponent reactions that allow the preparation of a variety of chemical compounds including peptides, heterocyclic compounds, or natural products. Here, the authors report enantioselective Ugi reactions that enable the synthesis of chiral α-acylamino amides and α-aminotetrazoles catalyzed by stereogenic-at-cobalt(III) complexes.
- Bing-Bing Sun
- , Kun Liu
- & Jie Yu
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Article
| Open Access
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
| Open Access
Ni-catalyzed carbamoylation of unactivated alkenes for stereoselective construction of six-membered lactams
Six-membered chiral lactams are common structural motifs of pharmaceuticals. Here, the authors describe a nickel-catalyzed reductive carbamoylation of alkenes to form enantioenriched six-membered lactams.
- Chenhuan Zhang
- , Xianqing Wu
- & Yifeng Chen
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Article
| Open Access
Enantioselective synthesis of α-aminoboronates by NiH-catalysed asymmetric hydroamidation of alkenyl boronates
Enantioenriched α-aminoboronic acid, a structural unit in many bioactive molecules, is also a valuable synthon in organic synthesis. Here, the authors disclose a NiH-catalysed asymmetric hydroamidation process for their direct synthesis.
- Yao Zhang
- , Deyong Qiao
- & Shaolin Zhu
Atroposelective synthesis of biaxial bridged eight-membered terphenyls via a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization of phenols