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Organocatalytic skeletal reorganization for enantioselective synthesis of S-stereogenic sulfinamides
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
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Article
| Open Access
“On-Water” accelerated dearomative cycloaddition via aquaphotocatalysis
Developing water compatible synthetic methods for Sulfur(VI) fluoride exchange (SuFEx) chemistry is of paramount importance. Here the authors demonstrate a catalytic dearomative [2+2] photocycloaddition that significantly speeds up the synthesis of heterocyclic alkyl SuFEx hubs, leveraging the unique reactivity at the water-oil interface.
- Soo Bok Kim
- , Dong Hyeon Kim
- & Han Yong Bae
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Article
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Catalytic 1,1-diazidation of alkenes
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
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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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Article
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Photo-modulated activation of organic bases enabling microencapsulation and on-demand reactivity
Oil-water emulsion techniques can be used for encapsulation of chemicals and control of reactivity, but is challenging for highly reactive materials such as acids and bases. Here, the authors report the encapsulation of bases by masking of reactivity with photo-removable protecting groups.
- Wenle Li
- , Xiaocun Lu
- & Nancy R. Sottos
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Article
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Chiral BINOL-phosphate assembled single hexagonal nanotube in aqueous solution for confined rearrangement acceleration
Supramolecular confined catalysis aims to mimic the active pocket of an enzyme to enhance the efficiency and selectivity of catalytic reactions. Here, the authors describe the formation of chiral nanotubes stable in aqueous solution employing a chiral BINOL-phosphate which can accelerate the 3-aza-Cope rearrangement by a nanotubular interior confinement effect.
- Kang Li
- , Wei-Min Qin
- & Yue-Peng Cai
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Article
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Dioxygen 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
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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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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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Unified 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
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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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Article
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Regio- and enantioselective synthesis of acyclic quaternary carbons via organocatalytic addition of organoborates to (Z)-Enediketones
All-carbon quaternary stereocenters are an important synthetic motif but are especially difficult to synthesize enantioselectively. Here, the authors demonstrate the organocatalytic regio- and enantioselective synthesis of valuable acyclic 1,4-dicarbonyl products with vinylated and arylated quaternary centers.
- Po-Kai Peng
- , Andrew Isho
- & Jeremy A. May
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Article
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Enabling nonconjugated polyesters emit full-spectrum fluorescence from blue to near-infrared
Near-infrared luminescence is useful for advance applications, but is challenging to achieve through clusteroluminescence. Here, the authors report the use of amine-initiated polyesters for amine-ester clusters with near-infrared emission.
- Bo Chu
- , Xiong Liu
- & Xing-Hong Zhang
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Article
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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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Organomediated electrochemical fluorosulfonylation of aryl triflates via selective C–O bond cleavage
Although aryl triflates are essential building blocks in organic synthesis, the applications as aryl radical precursors are limited. Here, the authors report an organomediated electrochemical strategy for the generation of aryl radicals from aryl triflates, providing a method for the synthesis of aryl sulfonyl fluorides from feedstock phenol derivatives under very mild conditions.
- Xianqiang Kong
- , Yiyi Chen
- & Zhong-Yan Cao
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Article
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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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Article
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Supramolecular catalysis with ethers enabled by dual chalcogen bonding activation
The activation of ethers by weak interactions in supramolecular catalysis remains challenging. Here, the authors describe an activation mode based on dual Se···π and Se···O bonding, that can activate benzylic as well as allylic ether C-O σ-bonds to achieve cyclization, coupling and elimination reactions.
- Zhiguo Zhao
- , Yuanling Pang
- & Yao Wang
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Article
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Catalytic enantioselective reductive alkynylation of amides enables one-pot syntheses of pyrrolidine, piperidine and indolizidine alkaloids
Saturated α-alkyl aza-heterocycles are found in a wide array of bioactive molecules. Here, the authors disclosed a one-pot, catalytic enantioselective synthesis of pyrrolidine, piperidine and indolizidine alkaloids from amides and alkynes.
- Fang-Fang Xu
- , Jin-Quan Chen
- & Pei-Qiang Huang
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Article
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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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Article
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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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Assembly drives regioselective azide-alkyne cycloaddition reaction
Metal-free versions of azide–alkyne cycloadditions could find widespread applications in biomedical contexts. Here, the authors report an assembly-driven, regioselective azide–alkyne cycloaddition.
- Qiaochu Jiang
- , Wenjun Zhan
- & Gaolin Liang
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Article
| Open Access
Integrating I(I)/I(III) catalysis in reaction cascade design enables the synthesis of gem-difluorinated tetralins from cyclobutanols
gem-Difluorinated motifs are prevalent in numerous leading pharmaceuticals. Here the authors merge I(I)/I(III)-catalysed fluorination and C(sp3)-F bond activation to generate these motifs directly from 1,3-diaryl cyclobutanols in a single operation.
- Joel Häfliger
- , Louise Ruyet
- & Ryan Gilmour
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Article
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Direct nucleophilic and electrophilic activation of alcohols using a unified boron-based organocatalyst scaffold
Boronic acids are promising catalysts for the direct functionalization of alcohols without requiring precious metals. Here, the authors report an easily synthesized class of cyclic hemiboronic acid catalysts which are applicable in both nucleophilic and electrophilic modes of alcohol activation.
- Jason P. G. Rygus
- & Dennis G. Hall
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Article
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Highly selective electrocatalytic alkynol semi-hydrogenation for continuous production of alkenols
Thermocatalytic alkynol semi-hydrogenation often uses high-pressure H2 and Pd-based catalysts. Here, using a Cu-based electrode, the authors investigate the electrocatalytic alkynol semi-hydrogenation to alkenols with water as the hydrogen source.
- Jun Bu
- , Siyu Chang
- & Jian Zhang
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Article
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Electricity-driven asymmetric bromocyclization enabled by chiral phosphate anion phase-transfer catalysis
Asymmetric electrochemical synthesis via ion-pairing catalysis is challenging due to interference of the electrolyte with the ion-pairing catalyst. Here, the authors describe a biphasic system to enable the asymmetric ion-pairing catalysis under electrochemical conditions.
- Xuefeng Tan
- , Qingli Wang
- & Jianwei Sun
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Article
| Open Access
Photocatalytic direct borylation of carboxylic acids
Boronic acids are useful reagents in organic synthesis and thus methods to prepare these compounds under mild conditions are desirable. Here, the authors synthesize boronic acids via photocatalytic decarboxylation of benzoic acids followed by borylation; guanidine-type additives are used to assist the process.
- Qiang Wei
- , Yuhsuan Lee
- & Zhibo Liu
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Article
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Chalcogen bond-guided conformational isomerization enables catalytic dynamic kinetic resolution of sulfoxides
Conformational isomerization of organic molecules can be guided by noncovalent interactions. Here, the authors report the synthesis of chiral sulfoxides catalyzed by N-heterocyclic carbenes; intramolecular chalcogen bonding interactions are key for conformational locking.
- Jianjian Liu
- , Mali Zhou
- & Yonggui Robin Chi
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Article
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Desymmetrization of N-Cbz glutarimides through N-heterocyclic carbene organocatalysis
Desymmetrization of achiral building blocks is one of the most efficient ways to access enantiopure compounds of synthetic relevance. Here, the authors desymmetrize glutarimides with alcohols via an imide C–N bond cleavage under NHC organocatalysis.
- Zhouli Hu
- , Chenlong Wei
- & Wei Huang
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Article
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Electroredox carbene organocatalysis with iodide as promoter
Oxidative carbene organocatalysis has been developed as a versatile synthetic method, but has been paired with electroredox chemistry in only limited examples. Herein, enantioenriched heterocycles are synthesized from racemic substrates via an iodide-promoted NHC organocatalysis system that is powered by electroredox chemistry.
- Peng Zhou
- , Wenchang Li
- & Tingshun Zhu
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Article
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Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones
The combination of carbene- and photocatalysis has enabled unorthodox routes to ketone syntheses, but usually requires engineered or activated substrates. Herein the authors present a carbene- and photocatalytic decarboxylative radical coupling of carboxylic acids and acyl imidazoles, in which the carboxylic acids are directly used as radical precursors.
- Shi-Chao Ren
- , Xing Yang
- & Yonggui Robin Chi
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Article
| Open Access
Efficient access to general α-tertiary amines via water-accelerated organocatalytic multicomponent allylation
The α-tertiary amine functional group is an essential structure of diverse naturally occurring alkaloids and pharmaceuticals. Here the authors show an efficient water-accelerated organocatalytic method to access α-tertiary amines incorporating homoallylic amine structures by exploiting ketones as useful starting material.
- Prithwish Goswami
- , Sung Yeon Cho
- & Han Yong Bae
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Article
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Organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover
Although electrochemical semipinacol rearrangements have been reported, a complementary photochemical route has yet to be developed. Here the authors report an organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover.
- Taiga Kodo
- , Kazunori Nagao
- & Hirohisa Ohmiya
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Article
| Open Access
Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation
The functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Here the authors show a transition-metal-free, radical relay π-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts.
- Jae Bin Lee
- , Gun Ha Kim
- & Sung You Hong
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Article
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Organocatalytic atroposelective construction of axially chiral N, N- and N, S-1,2-azoles through novel ring formation approach
1,2-Azoles are privileged structures in many natural products and drugs. The authors report an atroposelective synthesis of two types of axially chiral 1,2-azoles, through vinylidene ortho-quinone methide intermediates.
- Yu Chang
- , Chuandong Xie
- & Hailong Yan
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Article
| Open Access
Organocatalytic cycloaddition of alkynylindoles with azonaphthalenes for atroposelective construction of indole-based biaryls
There is great interest in methods for catalytic enantioselective construction of axially chiral compounds found in natural products. Here, the authors develop a cycloaddition strategy for atroposelective construction of indole-based biaryls via chiral phosphoric acid-catalysed cycloaddition.
- Hui Yang
- , Huai-Ri Sun
- & Ling Zhou
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Article
| Open Access
Asymmetric synthesis of N-bridged [3.3.1] ring systems by phosphonium salt/Lewis acid relay catalysis
Optically pure pseudo-natural products (PNPs) bearing N-bridged [3.3.1] ring systerm provide a platform for structure−activity relationship studies, but currently no examples of catalytic asymmetric strategies are available to construct such scaffolds. Here the authors show a general method for constructing such N-bridged [3.3.1] ring systems via a bifunctional phosphonium salt/Lewis acid relay catalysis.
- Jian-Ping Tan
- , Kehan Li
- & Tianli Wang
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Article
| Open Access
Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation
Nitriles have proven to be useful functional groups in pharmaceuticals and polymers, both as active moieties themselves or as easy precursors to further transformations, but synthesis of benzonitriles with axial chirality has often been difficult. Here the authors make axially chiral benzonitriles via N-heterocyclic carbene organocatalysis via a dynamic kinetic resolution process.
- Ya Lv
- , Guoyong Luo
- & Yonggui Robin Chi
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Article
| Open Access
Enantioselective access to tricyclic tetrahydropyran derivatives by a remote hydrogen bonding mediated intramolecular IEDHDA reaction
Although the hetero-Diels–Alder reaction is a staple of organic chemistry, catalytic asymmetric versions of the inverse-electron demand variant often require specially engineered substrates for the reaction to work. Here the authors cyclize non-activated alkenes with α,β-unsaturated ketones or aldehydes to form chiral fused heterocycles using a chiral phosphoric acid catalyst.
- Min Jin
- , Congyun Tang
- & Liang-Liang Wang
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Article
| Open Access
Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization
One-pot/one-step polymerizations are ideal with regards to efficiency and simplicity of copolymerization, but can be difficult for the practitioner to control. Here the authors perform one-pot/one-step polymerizations with three monomers, producing diblock dialternating terpolymers with precise alternating structure.
- Jiaxi Xu
- , Xin Wang
- & Nikos Hadjichristidis
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Article
| Open Access
Asymmetric biomimetic transamination of α-keto amides to peptides
Asymmetric transamination of
α -keto amides could provide an efficient strategy to synthesise peptides, but has not been well developed yet. Here, the authors design chiral pyridoxamine catalyst and realize the asymmetric biomimetic transamination of α-keto amides, providing access to various peptides with excellent enantiopurities.- Weiqi Cai
- , Xuelong Qiao
- & Baoguo Zhao
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Article
| Open Access
Aryl radical-mediated N-heterocyclic carbene catalysis
Use of aryl halides as coupling precursors typically occurs through transition metal catalysis and/or photoredox chemistry, which requires some combination of light, metals, and oxidants or reductants. Here, the authors show a method to generate aryl radicals from halides using only an NHC organocatalyst.
- Yuki Matsuki
- , Nagisa Ohnishi
- & Hirohisa Ohmiya
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Article
| Open Access
Chemoselective catalytic hydrodefluorination of trifluoromethylalkenes towards mono-/gem-di-fluoroalkenes under metal-free conditions
Fluorine-containing moieties show significant effects in improving the properties of functional molecules. Here the authors show diazaphospholene-catalyzed hydrodefluorination of trifluoromethylalkenes to chemoselectively construct gem-difluoroalkenes and terminal monofluoroalkenes by simple adjustment of the reactant stoichiometry.
- Jingjing Zhang
- , Jin-Dong Yang
- & Jin-Pei Cheng
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Article
| Open Access
Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives
1-(Isoquinolin-1-yl)naphthalen-2-ol (QUINOL) is an atropisomeric heterobiaryl that serves as a platform for the synthesis of other biaryl ligands useful in asymmetric catalysis. Here, the authors report a straightforward oxidative cross-coupling reaction between isoquinolines and 2-naphthols to efficiently access the QUINOL scaffolds in a metal-free manner.
- Peng-Ying Jiang
- , Kai-Fang Fan
- & Bin Tan
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Article
| Open Access
Benzylic C−H acylation by cooperative NHC and photoredox catalysis
Direct acylation of sp3 C−H bonds in complex organic molecules is not well established compared to that of sp2 C−H bonds. Here, the authors report the combination of N-heterocyclic carbene (NHC) and photoredox catalysis for the direct and site-selective acylation of benzylic C−H bonds.
- Qing-Yuan Meng
- , Lena Lezius
- & Armido Studer
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Article
| Open Access
Direct catalytic asymmetric synthesis of α-chiral bicyclo[1.1.1]pentanes
Bicyclo[1.1.1]pentanes (BCPs) are important motifs in contemporary drug design, however, approaches to BCPs featuring adjacent stereocenters are rather limited. Here, the authors report a photo- and organocatalyzed asymmetric addition of simple aldehydes to [1.1.1]propellane to generate enantioenriched α-chiral BCPs.
- Marie L. J. Wong
- , Alistair J. Sterling
- & Edward A. Anderson
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Article
| Open Access
Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether
The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) enrich the toolbox to prepare well-defined polypeptide materials. Here the authors use crown ethers to catalyze the polymerization of NCA initiated by conventional primary amine initiators in solvents with low polarity and low hydrogen-bonding ability.
- Yingchun Xia
- , Ziyuan Song
- & Jianjun Cheng
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Article
| Open Access
Unified divergent strategy towards the total synthesis of the three sub-classes of hasubanan alkaloids
Several Hasubanan alkaloids have been synthesized in the past decades, however a divergent approach to access the 3 subclasses of such natural products has not been reported yet. Here, the authors show the enantioselective total syntheses of four representative members via a unified strategy leading to the three topologically different classes of alkaloids.
- Guang Li
- , Qian Wang
- & Jieping Zhu
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Article
| Open Access
Chiral phosphoric acid-catalyzed stereodivergent synthesis of trisubstituted allenes and computational mechanistic studies
Despite of the high demand of chiral allenes, their asymmetric synthesis remains a challenge for organic chemists. Here, the authors report a stereodivergent synthesis of trisubstituted allenes via asymmetric additions of oxazolones to activated 1,3-enynes enabled by modification of chiral phosphoric acid catalysts.
- Jiawen Wang
- , Sujuan Zheng
- & Xiaoyu Yang
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Article
| Open Access
A robust and tunable halogen bond organocatalyzed 2-deoxyglycosylation involving quantum tunneling
Halogen bonding (HB) catalysis is rapidly gaining momentum, however, cases of XB activation for challenging bonds formation are rare. Here, the authors show a robust XB catalyzed 2-deoxyglycosylation with broad scope and featuring a quantum tunneling phenomenon in the proton transfer rate determining step.
- Chunfa Xu
- , V. U. Bhaskara Rao
- & Charles C. J. Loh
Catalytic asymmetric synthesis of planar-chiral dianthranilides via (Dynamic) kinetic resolution