Article
Chemistry, Multidisciplinary
Lin-Jun Qi, Cui-Ting Li, Zheng-Qi Huang, Jia-Tian Jiang, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: The study presents a novel copper-catalyzed asymmetric formal annulation reaction, which can synthesize a range of chiral oxygen-heterocycles via carbonyl ylides with excellent enantioselectivity and yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Toktam S. Shirazian, Hossein Zahedian Tejeneki, Ali Nikbakht, Frank Rominger, Saeed Balalaie
Summary: This study presents a novel method for synthesizing functionalized acridines using a base-promoted formal [4+2] cycloaddition reaction. The method exhibits high selectivity and efficiency, making it a valuable approach for the synthesis of acridine backbones.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Na Li, Bing Hu, Xinying Zhang, Xuesen Fan
Summary: A controlled and selective construction of spiro or fused heterocyclic scaffolds can be achieved through one-pot cascade reactions of 1-phenylpyrazolidinones with maleimides. The reactions involve C-H bond activation/functionalization, intramolecular cyclization, and traceless fusion of the pyrazolidinonyl unit to form succinimide spiro pyrazolo[1,2-a]pyrazolones or succinimide-fused pyrazolidinonylcinnolines. These protocols offer easily tunable selectivity, broad substrate scope, cost-effective and sustainable oxidant, excellent atom economy, and facile scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Pavel Yu Ushakov, Sema L. Loffe, Alexey Yu Sukhorukov
Summary: This review summarizes the advancements made in [4 + 1]-annulation reactions involving sulfonium, sulfoxonium, and ammonium ylides, as well as diazo compounds and carbenes over the past six years. The newly emerged methods for generating A(4)-synthons, such as radical, transition metal-catalyzed, and photo-redox processes, are outlined. Specific focus is given to the progress in asymmetric [4 + 1]-annulations using organocatalysis and chiral ammonium ylides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Marta Solas, Lorena Renedo, Samuel Suarez-Pantiga, Roberto Sanz
Summary: A gold-catalyzed cascade double cyclization reaction was developed for the synthesis of heterobiaryl compounds, such as furanyl and pyrrolyl 2H-chromenes, from readily available starting materials derived from biomass platform molecules. The reaction involves an initial heterocyclodehydration step followed by an alkyne hydroarylation to form the chromene core.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Xuling Chen, Pengfei Li
Summary: Benefiting from the rapid development of MBH reaction, the reaction of MBH adducts has become one of the most synthetically useful transformations. However, the (1+4)-annulations of MBH adducts have not developed rapidly until recently, compared with the well-established allylic alkylations and (3+2)-annulations. As a beneficial complement to the (3+2)-annulations, the (1+4)-annulations of MBH adducts provide a robust access to structurally diverse five-membered carbo- and heterocycles. This paper summarizes recent advances in organocatalytic (1+4)-annulations using MBH adducts as 1 C-synthons for the construction of functionalized five-membered carbo- and heterocycles.
Review
Biochemistry & Molecular Biology
Kashaf Babar, Ameer Fawad Zahoor, Sajjad Ahmad, Rabia Akhtar
Summary: The synthesis of spirocyclic compounds has garnered attention from synthetic chemists for their privileged ring system and efficacy in drug discovery. Many natural compounds with spirocyclic moieties are effective in the pharmaceutical industry. Recent synthetic methodologies have been established for constructing various spirocompounds containing six-membered carbocycles/heterocycles.
MOLECULAR DIVERSITY
(2021)
Article
Chemistry, Organic
Gulshan Kumar, Mithilesh Nagpure, Vajja Krishna Rao, Sankar K. Guchhait
Summary: A (4+1)-annulation reaction between arylidene heterocyclic-N-fused imidazolones and alpha-carbonyl sulfoxonium ylides has been developed, allowing the efficient synthesis of various N-heterocycle-fused furans, which are important structural components in secondary hydroxyls and drug/bioactive compounds. This study explores the unique triple-role of alpha-carbonyl sulfoxonium ylides and the characteristic stereo-electronic functional behavior of arylidene N-fused imidazolones.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bang-An Zhou, Chun-Lin Zhang, Song Ye
Summary: Researchers have developed an NHC-catalyzed benzannulation reaction for the synthesis of benzotrifluorides using enals and beta-trifluoromethylenones. This reaction involves a [4 + 2] annulation/lactonization/decarboxylation/oxidative aromatization cascade catalyzed by NHC. The reaction shows mild conditions, excellent functional group compatibility, and exclusive regioselectivity, resulting in the formation of multi-substituted benzotrifluorides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yun Sa, Xin Lv, Jia-Yu Yao, Xu-Yang Lu, Ai-Bin Wu, Wen-Ming Shu, Wei-Chu Yu
Summary: A tandem reaction for the synthesis of phenanthrenes from arynes and alpha-(bromomethyl)styrenes is reported. The reaction proceeds via an ene reaction of alpha-(bromomethyl)styrenes with arynes, followed by a [4 + 2] cycloaddition reaction. The reaction generates 9-benzylphenanthrene derivatives in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hai-Ying Wang, Zhi-Cheng Li, Chun-Lin Zhang, Song Ye
Summary: A NHC-catalyzed method for the atroposelective synthesis of axially chiral α-carbolinones from α,β-unsaturated iminoindole derivatives and α-chloroaldehydes was developed. The reaction involves a cascade process including [4 + 2] annulation and oxidative dehydrogenation, leading to a conversion of central-to-axial chirality under mild conditions. The developed method offers a new avenue for the efficient synthesis of axially chiral α-carbolinones with moderate to good enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Gang Yang, Lin Yao, Guojiang Mao, Guo-Jun Deng, Fuhong Xiao
Summary: We have reported a metal-free protocol for the synthesis of indenoquinolinones and 2-substituted quinolines via [4 + 2] cycloaddition reaction using readily available 2-aminobenzaldehydes and ketones as starting materials. Different quinoline derivatives can be selectively synthesized by changing the type of ketones. O-2 and dimethyl sulfoxide (DMSO) as co-oxidants play an important role in the synthesis of indenoquinolinones. This condensation/oxidation strategy involves the formation of C-N, C-C, and C-O bonds, with the advantages of high yields and a broad substrate range.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Gang Yang, Lin Yao, Guojiang Mao, Guo-Jun Deng, Fuhong Xiao
Summary: A metal-free protocol for the synthesis of indenoquinolinones and 2-substituted quinolines using readily available 2-aminobenzaldehydes and ketones has been reported. Different quinoline derivatives can be selectively synthesized by altering the type of ketones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Simiao Zhang, Chen Lin, Chaolei Liu, Ding Du
Summary: An efficient synthetic approach using N-heterocyclic carbene catalysis was developed to access a wide range of enantioenriched structurally interesting delta-carbolinones under mild reaction conditions through a formal [3+3] annulation of 3-aminoindoles with 2-bromoenals.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Simiao Zhang, Chen Lin, Chaolei Liu, Ding Du
Summary: This study achieved the enantioselective synthesis of a series of enantioenriched and structurally interesting delta-carbolinones through a new synthetic method, offering new possibilities in the field of organic synthetic chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yang Gao, Simin Yang, Minwei She, Jianhong Nie, Yanping Huo, Qian Chen, Xianwei Li, Xiao-Qiang Hu
Summary: We report a practical route for the synthesis of valuable 3-aryl anthranils from readily available anthranils and simple arenes using electrophilic aromatic substitution (EAS) strategy. The method shows good compatibility with a wide range of arenes and delivers various structurally diversified 3-aryl anthranils in good yields and high regioselectivity. The synthesized 3-aryl anthranils are proven to be a highly robust platform for accessing biologically active compounds, drug derivatives, and organic optoelectronic materials.
Article
Chemistry, Organic
Qian-Ci Gao, Yi-Fei Li, Jun Xuan, Xiao-Qiang Hu
Summary: Herein, we report an unprecedented Rh(III)-catalyzed C-H activation/annulation cascade of readily available enaminones with iodonium ylides towards the convenient synthesis of isocoumarins. This coupling system proceeds in useful chemical yields (up to 93%) via a cascade C-H activation, Rh-carbenoid migratory insertion and acid-promoted intramolecular annulation. The success of gram-scale reaction and diverse functionalization of isocoumarins demonstrated the synthetic utility of this protocol.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yang Gao, Haixia Li, Yupeng Zhao, Xiao-Qiang Hu
Summary: This highlight summarizes recent progress on catalytic nitrene transfer reactions using hydroxylamine derivatives as prevalent precursors. The key features of these N-O derived nitrene transfer reagents are their ready availability, stability, and ease of activation by a range of transition metal-catalysts under mild conditions. Their application in transition metal-catalysis has led to numerous new amidation or amination reactions, such as C-H insertions and aziridination of olefins. These reagents have also found utility in the difunctionalization of unsaturated bonds, dearomative amination of indoles, and formation of N-X bonds. Moreover, the recent achievements in photocatalysis and enzyme catalysis further highlight the importance of these appealing reagents.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Li-Jing Li, Zhong-Qiang Zhou, Zi-Kui Liu, Yuan-Yuan He, Feng-Cheng Jia, Xiao-Qiang Hu
Summary: An unprecedented DMAP-catalysed amidation of aryl and alkyl carboxylic acids with organo-cyanamides has been developed, revealing an unusual desulfonylation/decyanation reaction model. This reaction possesses remarkable features such as readily available substrates, simple operation, and broad scope, enabling the efficient synthesis of structurally diverse amides.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Peng-Zi Wang, Wen-Jing Xiao, Jia-Rong Chen
Summary: Creating, conserving, and modifying the stereochemistry of organic compounds is an important area of research in synthetic chemistry. Stereochemical editing, as an alternative strategy, allows for late-stage alteration of stereochemistry, but it often faces thermodynamic barriers. Photocatalysis, by using photogenerated radical species, can overcome these barriers and enable contra-thermodynamic stereochemical editing processes.
NATURE REVIEWS CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Peng-Zi Wang, Wen-Jing Xiao, Jia-Rong Chen
Summary: A general electrochemical strategy has been developed for the direct C-H carboxylation of N-heteroarenes with CO2, resulting in carboxylated products with excellent and tunable site selectivity. This study also opens up possibilities for regulating reactivity modes in electrochemical synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xue-Song Zhou, Zhihan Zhang, Wen-Yuan Qu, Xiao-Peng Liu, Wen-Jing Xiao, Min Jiang, Jia-Rong Chen
Summary: We report a cooperative catalytic system comprising a chiral nickel Lewis acid catalyst and an organic photocatalyst fueled by visible-light irradiation that allows for the hitherto elusive asymmetric [3 + 2] photocycloaddition of β-keto esters with vinyl azides under redox-neutral conditions. This protocol enables highly enantioselective construction of polycyclic densely substituted 3,4-dihydro-2H-pyrrole heterocycles featuring two contiguous tetrasubstituted carbon stereocenters, including a useful chiral N,O-ketal motif that is not easily accessible with other catalytic methods. Mechanistic studies revealed that the overall reactivity relies on the seamless integration of dual roles of nickel catalysts by the catalytic formation of the substrate/Ni complex, assisting both photoredox event and enantioselective radical addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yupeng Zhao, Yang Gao, Zhongke Xie, Shuwei Liao, Jiebin Huang, Yanping Huo, Qian Chen, Xianwei Li, Xiao-Qiang Hu
Summary: Different chemoselectivities were observed between phenols and thiophenols in the Tf2O-promoted C3 functionalization of simple anthranils. Phenols and anthranils react to form 3-aryl anthranils via a C-C bond formation, while thiophenols form 3-thio anthranils through a C-S bond formation. Both reactions have a broad substrate scope and tolerate a wide range of functional groups, yielding the corresponding products with specific chemoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
News Item
Chemistry, Multidisciplinary
Peng-Zi Wang, Jia-Rong Chen
Summary: In this study, N-N pyridinium ylides were used to generate triplet state diradicals through photoinduced energy transfer, and subsequent [3+2] cycloaddition with a tethered alkene allowed the synthesis of diverse ortho-pyridyl lactams.
Article
Chemistry, Organic
Guang-Da Xia, Zi-Kui Liu, Yu-Lian Zhao, Feng-Cheng Jia, Xiao-Qiang Hu
Summary: The synthesis of tertiary phosphines(III) has been a long-standing challenge in synthetic chemistry due to issues including harsh conditions, sensitive organometallic reagents, and pre-functionalized substrates. In this study, a strategically novel C(sp(3))-H bond phosphorylation method is reported, which allows for the synthesis of structurally diverse tertiary phosphines(III) from industrial phosphine(III) sources under mild photocatalytic conditions. The combination of ligand-to-metal charge transfer (LMCT) and hydrogen atom-transfer (HAT) process enables the generation of alkyl radicals from hydrocarbons. Furthermore, this catalytic system can also be applied for the polymerization of electron-deficient alkenes.
Article
Chemistry, Multidisciplinary
Xue-Song Zhou, Zhihan Zhang, Wen-Yuan Qu, Xiao-Peng Liu, Wen-Jing Xiao, Min Jiang, Jia-Rong Chen
Summary: We report a cooperative catalytic system that enables the elusive asymmetric [3 + 2] photocycloaddition of beta-keto esters with vinyl azides under redox-neutral conditions, using a chiral nickel Lewis acid catalyst and an organic photocatalyst fueled by visible-light irradiation. This protocol allows for the highly enantioselective construction of polycyclic densely substituted 3,4-dihydro-2H-pyrrole heterocycles featuring two contiguous tetrasubstituted carbon stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Guo-Qing Li, Fan-Rong Meng, Wen-Jing Xiao, Jia-Rong Chen
Summary: Catalytic radical difunctionalization of 1,3-enynes is a promising method for constructing valuable allenes and propargylic compounds. However, there has been limited progress in enantioselective radical 1,2-difunctionalization. In this study, a regio- and enantioselective radical three-component coupling of 1,3-enynes, oxime esters, and carboxylic acids through photoinduced copper catalysis is reported. This protocol demonstrates excellent enantioselectivity and provides access to a library of cyanoalkylated propargylic esters.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zhen-Wei Sun, Na Luo, Xiang Zhang, Wen-Jun Tuo, Xiao-Qiang Hu, Feng-Cheng Jia
Summary: A copper-catalyzed tandem cyclization reaction was developed for the efficient synthesis of pyrimidoquinazolinones using readily available 4-bromoisatins and amidine hydrochlorides. This reaction combined Ullmann-type cyclization and ring expansion by utilizing bimolecular amidine salts. It features simple operation, mild conditions, a wide substrate range, and scalability for multigram synthesis. Control experiments and detection of key intermediates provided support for the reaction mechanism.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Guoqing Li, Jiarong Chen
Summary: In this study, a highly efficient, selective and atom-economical method for the construction of allylic amines is reported. The combination of a photoredox catalyst and cobaloxime catalyst enables site-selective allylic amination of various olefins with secondary alkyl amines, resulting in valuable tertiary aliphatic allylamines without the need for external oxidants.
GREEN SYNTHESIS AND CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ji-Hang Xu, Zi-Kui Liu, Yan-Liu Tang, Yang Gao, Xiao-Qiang Hu
Summary: An unprecedented ring-opening cross-coupling of 1,2-oxazetidines with arylboronic acids using copper catalysis has been achieved. This reaction offers simple operation, inexpensive catalyst, broad scope, and high regioselectivity, leading to a wide range of aminomethylation products. Furthermore, the obtained products can be further transformed and bioactive acids can be modified.
CHEMICAL COMMUNICATIONS
(2022)
