Default Latest Most Read Please wait a minute... REVIEWS Z∶E Selective Preparation of Disubstituted Internal Alkenes and Trisubstituted Alkenes Ping Guo, Yong Zhou, Jie Zhao Chinese Journal of Organic Chemistry 2023, 43 (3): 855-872. DOI: 10.6023/cjoc202212039 Published: 01 March 2023 Abstract (895) HTML (52) PDF (1184KB)(1087) Knowledge map Olefin is one of the most important bulk chemicals in industry as well as commonly used starting materials in pharmaceutical field. Since Z-olefins and E-olefins exhibit great differences in physicochemical properties and biological activities, the Z∶E configuration control has been playing important roles in olefin preparation. The selective synthetic methods of Z∶E configurations of disubstituted inner alkenes and trisubstituted alkenes are reviewed, including the Wittig reaction, substituted alkane elimination reaction, olefin isomerization reaction, olefin metathesis, olefin coupling reaction, and alkyne addition reaction. The catalyst types and controlling factors of Z∶E selectivity in these synthetic examples are described in detail. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES N-Heterocyclic Carbene (NHC)-Catalyzed [4+3] Cycloaddition to Synthesize 4-Aminobenzoheptenolactons Chunbo Dai, Siqi Xia, Xiaoyu Chen, Limin Yang Chinese Journal of Organic Chemistry 2023, 43 (3): 1084-1090. DOI: 10.6023/cjoc202301011 Published: 01 March 2023 Abstract (513) HTML (34) PDF (1050KB)(786) Knowledge map A highly efficient N-heterocyclic carbene (NHC) catalyzed formal [3+4] cycloaddition reaction of γ-chloroenal with iminoquinones has been developed, producing 4-aminobenzoheptenolactone derivatives in good yields. In order to explore the role of nitroheterocyclic carbene in the site selectivity of the reaction, a theoretical study was carried out using density functional theory. The study showed that the deformation force was the main reason for the difference in site selection. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Research Progress of Reaction-Based Probes for Detecting Fluoride Ion Yanjie Qu, Yajun Li, Hongli Bao Chinese Journal of Organic Chemistry 2023, 43 (3): 809-825. DOI: 10.6023/cjoc202302015 Published: 01 March 2023 Abstract (574) HTML (40) PDF (1644KB)(1114) Knowledge map Fluoride ion is closely related to human life activities. Excessive or too little fluoride ions in human body will cause pathological changes. Therefore, it is necessary to develop appropriate measures to detect the fluoride ion content in human body and environment. Colorimetry and fluorescence detection have attracted much attention due to their high selectivity, high sensitivity and fast response. Herein, reaction-based fluoride ion probes are introduced. According to the reaction mechanisms, these probes can be divided into five types: interactions between fluoride ion and boronic acid derivatives, fluoride ion-promoted cleavage of Si—C bond, fluoride ion-promoted cleavage of Si—O bond, fluoride ion-induced dehydrogenation, fluoride ion-promoted cleavage of P—O bond. Not only the detection method of the probe is introduced, but also the action mechanism of some examples is described. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Copper-Catalyzed Allylic C(sp3)—H Sulfonylation of Cyclic Olefins Chunyang Liu, Yan Li, Qian Zhang Chinese Journal of Organic Chemistry 2023, 43 (3): 1091-1101. DOI: 10.6023/cjoc202211028 Published: 01 March 2023 Abstract (579) HTML (32) PDF (587KB)(657) Knowledge map A highly efficient copper-catalyzed direct sulfonylation of allylic C(sp3)—H bond was developed using simple cyclic olefins and sodium sulfite as starting materials. A series of allylic sulfone derivatives were synthesized in moderate to good yields under mild conditions. The mechanism study shows that the reaction might involve radical intermediates. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Recent Advances of Efficient Synthesis of Chiral Molecules Promoted by Pd/Chiral Phosphoric Acid Synergistic Catalysis Xun Xiang, Zhaolin He, Xiuqin Dong Chinese Journal of Organic Chemistry 2023, 43 (3): 791-808. DOI: 10.6023/cjoc202211043 Published: 01 March 2023 Abstract (887) HTML (70) PDF (1005KB)(1184) Knowledge map Transition metal palladium-catalyzed asymmetric reaction is an important and efficient method to synthesize chiral compounds. It has made considerable progress and achieved great success in the past decades. However, some reactions could not achieve high reactivity and excellent stereoselectivity just promoted by transition metal palladium catalysis. Therefore, it is of great significance to combine transition metal palladium catalysis and organocatalysis, which could be conducive to dissolve these challenging problems and received great attention. In recent years, a variety of asymmetric catalytic reactions have been efficiently realized by the synergistic catalysis system of transition metal palladium catalysis and chiral phosphoric acids with high chemo-, regio-, and stereoselectivity, and considerable research results and some important breakthroughs have been achieved. The recent progress of asymmetric allylation reaction, C(sp3)—H, C(sp2)—H functionalization and other reactions promoted by this synergistic catalysis system is summarized, the interaction between catalysts and substrates is systematically analyzed, and the influence factors of reactivity and selectivity are deeply discussed. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Recent Advances in the Synthesis of Fused Heterocyclic Compounds and Their Antitumor Activities Kanghui Duan, Junlong Tang, Wanqing Wu Chinese Journal of Organic Chemistry 2023, 43 (3): 826-854. DOI: 10.6023/cjoc202211046 Published: 01 March 2023 Abstract (776) HTML (59) PDF (1385KB)(1117) Knowledge map The unique physicochemical properties invest fused heterocyclic compounds with wide applications in the synthesis of natural products, drugs, superconducting materials, energy storage materials, polymer materials, organic dyes, etc. In recent years, the rapid development of transition metal-catalyzed reactions of unsaturated hydrocarbons has developed rapidly. Owing to the advantages of high step- and atom-economy, easy availability of raw starting materials, and efficient construction of carbon-carbon bonds or/and carbon-hetero bonds, it is a vital way to synthesize fused heterocyclic compounds. Herein, the recent progress on the reaction development of transition metal-catalyzed cyclizations involving unsaturated hydrocarbons for the synthesis of fused heterocyclic compounds including benzofurans, indoles, quinolines in the last five years has been summarized, as well as their applications in the field of medicinal chemistry with antitumor activities. Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Nickel-Catalyzed Enantioselective Hydrosilylation of 1,1-Disubstituted Allenes Shaowei Chen, Xiao Shen Chinese Journal of Organic Chemistry 2023, 43 (3): 1213-1214. DOI: 10.6023/cjoc202300018 Abstract (506) HTML (23) PDF (374KB)(480) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Photoinduced Gold-Catalyzed Divergent Dechloroalkylation of gem-Dichloroalkanes Peizhuo Lü, Yuanhong Liu Chinese Journal of Organic Chemistry 2023, 43 (3): 1206-1207. DOI: 10.6023/cjoc202300015 Abstract (306) HTML (17) PDF (648KB)(509) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Asymmetric Construction of Axially Chiral Arylpyrazole-Based Phosphorus Frameworks by Dipeptide-Phosphonium Salt Catalysis Ziqi Zhu, Feng Shi Chinese Journal of Organic Chemistry 2023, 43 (3): 1208-1210. DOI: 10.6023/cjoc202300016 Abstract (294) HTML (22) PDF (479KB)(426) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Cobalt-Catalyzed Nitrogen Atom Insertion and Ring Expansion of Cycloalkenes Baoying Zhu, Lingbo Qu, Conghui Tang Chinese Journal of Organic Chemistry 2023, 43 (3): 1211-1212. DOI: 10.6023/cjoc202300017 Abstract (505) HTML (23) PDF (355KB)(577) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Copper(I)-Catalyzed Asymmetric Conjugate Addition of 1,4-Dienes to β-Substituted Alkenyl Azaarenes Yanli Yin, Zhiyong Jiang Chinese Journal of Organic Chemistry 2023, 43 (3): 1203-1205. DOI: 10.6023/cjoc202300014 Abstract (580) HTML (19) PDF (402KB)(337) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Visible Light-Catalyzed Synthesis of Difluoroalkylated Polycyclic Indoles Jinxiao Zhao, Tonghui Wei, Sen Ke, Yi Li Chinese Journal of Organic Chemistry 2023, 43 (3): 1102-1114. DOI: 10.6023/cjoc202212032 Published: 23 February 2023 Abstract (430) HTML (30) PDF (845KB)(644) Knowledge map Polycyclic indoles are widely found in natural products and pharmaceutical molecules, and have a wide range of applications in the pharmaceutical, pesticide and dye industries. Although considerable development has been made in the synthesis of indole polycycles, it is still of great scientific interest and value to explore more efficient and milder experimental strategies for the synthesis of highly-functionalized polycyclic indoles. Herein, a one-step radical tandem cyclization reaction to synthesize difluoroalkylindoles with quaternary carbon centers by using difluorobromoesters as the fluorine source and 3-alkenyl indoles as the substrates under visible light-catalyzed conditions was developed. The method is easy-to-operate and mild in conditions, with a wide range of substrate adaptability and good yields, providing a green and efficient synthetic route for fluorine-containing polycyclic indoles. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Research Progress on Synthesis of Thioflavonoids Ling Meng, Jun Wang Chinese Journal of Organic Chemistry 2023, 43 (3): 873-891. DOI: 10.6023/cjoc202301004 Published: 23 February 2023 Abstract (606) HTML (56) PDF (1028KB)(1108) Knowledge map Thioflavonoids are the sulfur counterparts of flavonoids, which have a wide range of applications in the fields of medicine, material science, organic synthesis and others. Therefore, it is of great significance to develop efficient synthetic methods to obtain thioflavonoids with diverse structures. The synthetic approaches of thioflavonoids and key steps of reaction mechanisms according to the classification of thioflavonoids are summarized, and the development prospect of this research field is prospected. Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Selective Formal Carbene Insertion into C—B Bonds of Diboronates Xin Li, Qiuling Song Chinese Journal of Organic Chemistry 2023, 43 (3): 1197-1198. DOI: 10.6023/cjoc202300011 Abstract (429) HTML (24) PDF (376KB)(544) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Alternating Current Promoted Silver Catalysis for C—H Phosphorylation Na Chen, Haichao Xu Chinese Journal of Organic Chemistry 2023, 43 (3): 1199-1200. DOI: 10.6023/cjoc202300012 Abstract (251) HTML (17) PDF (348KB)(499) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Copper-Catalyzed Enantioselective Radical Heteroatomic S—O Cross-Coupling Yuxuan Han, Xiuling Cui Chinese Journal of Organic Chemistry 2023, 43 (3): 1201-1202. DOI: 10.6023/cjoc202300013 Abstract (257) HTML (13) PDF (387KB)(409) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Application of Ligands in Cp*Rh(III)-Catalyzed C—H Bond Functionalization Reaction Yannian Pan, Xiao Qin, Chengkai Yuan, Yi Lu Chinese Journal of Organic Chemistry 2023, 43 (3): 924-948. DOI: 10.6023/cjoc202211039 Published: 15 February 2023 Abstract (636) HTML (45) PDF (1175KB)(957) Knowledge map Cp*Rh(III) catalysts have shown excellent performance in the field of inert C—H bond functionalization because of their high activity and stability under mild conditions. However, limited by the number of Rh(III) coordination orbitals, the ligand studies in Cp*Rh(III) catalytic system are relatively few. Recently, our research group has been focusing on the external ligands promoted C—H bond functionalization with high activity and selectivity. In this review, the related works of Cp*Rh(III) catalyzed C—H bond functionalization are systematically summarized, including both symmetric and asymmetric C—H activation, the role of ligands in the Cp*Rh(III) catalytic system is discussed, and some reaction mechanisms are briefly described. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Recent Progress in Transition Metal Catalyzed C(sp3)—H Nitrene Insertion Reactions Assisted by Directing Groups Xing Yang, Xu Liu, Lijia Wang Chinese Journal of Organic Chemistry 2023, 43 (3): 914-923. DOI: 10.6023/cjoc202211041 Published: 15 February 2023 Abstract (571) HTML (40) PDF (706KB)(989) Knowledge map The transition metal catalyzed activation of C(sp3)—H bonds to form carbon-nitrogen bonds has been a challenging and hot research area. The transition metal-catalyzed C(sp3)—H amination strategy provides a more direct and efficient way to form C—N bonds. With the vigorous development in the field of C—H bond activation, a variety of directing groups and transition metal catalyst systems have been developed, which provide effective tools for C(sp3)—H amination through the inner sphere mechanism. In recent years, important progress has been made in directing group-assisted C(sp3)—H bond amination reactions, and many catalyst systems based on different transition metals with cheap and efficient amination reagents have been developed. The research progress of transition metal-catalyzed C(sp3)—H nitrene insertion reaction assisted by directing groups in the past decade is reviewed. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Recent Advances on Catalytic Enantioselective Protonation for Construction of α-Tertiary Carbonyl Compounds Weidi Cao, Xiaohua Liu Chinese Journal of Organic Chemistry 2023, 43 (3): 961-973. DOI: 10.6023/cjoc202211045 Published: 15 February 2023 Abstract (793) HTML (29) PDF (1001KB)(1061) Knowledge map Catalytic enantioselective protonation (EP) is a straightforward and effective approach to construct enantioenriched carbonyl compounds containing a tertiary stereocenter at its α-position, which has been widely applied in organic synthesis and medicinal chemistry. This field has significant advances in recent decades, and relevant reviews based on substrate category, catalytic system and reaction type have been reported successively. In this paper, new developments in this field are updated and summarized since 2019, which are classied into the directly catalytic asymmetric protonation of performed enolates and the enantioselective protonation of in situ enolates, α-carbanion, or α-radical intermediates, involving a variety of substrate categories, catalytic systems, activation modes, as well as catalytic strategies and means. It is expected that these studies can inspire chemists to continuously contribute to this field and further promote the development of carbonyl chemistry, asymmetric catalysis and other related fields, and provide facile and efficient access to high-value chiral molecules, including natural products and their intermediates, drugs, drug candidates and so on. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Research Progress of Lewis Acid and Base Pairs Applied in Materials Chemistry Lijuan Xiao, Yanping Zhang, Miao Hong Chinese Journal of Organic Chemistry 2023, 43 (3): 949-960. DOI: 10.6023/cjoc202301009 Published: 15 February 2023 Abstract (725) HTML (45) PDF (1007KB)(865) Knowledge map Lewis Pairs (LPs) have made a rapid development in the fields of small molecule activation (such as CO2, H2, CO, SO2, N2O) and asymmetric catalysis, mainly thanks to the diversity of Lewis Pairs (LPs) synthesis and the convenient tunability of steric hindrance and electronic effects. The synthesis of novel functional polymer materials has always been a research hotspot in material chemistry. The introduction of Lewis acids (LAs) and Lewis bases (LBs) into the polymer skeleton can endow materials with unique properties and greatly enrich the types of functional polymer materials. Herein, this review summarizes the recent advance and synthesis of macro-LAs and macro-LBs, but also illustrates the diversity and versatility of LPs and Lewis pair polymerizations (LPPs) in the application of material chemistry. This review highlights the construction of supramolecular polymer networks, CO2 capture and release, and the synthesis of novel topological polymers. In addition, the challenges and the future development trend in this field are also proposed. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Research Progress in Ortho-C—H Bond Functionalization of Rylene Diimides Kongchuan Wu, Kaihong Lu, Jianbin Lin, Huijun Zhang Chinese Journal of Organic Chemistry 2023, 43 (3): 1000-1011. DOI: 10.6023/cjoc202211042 Published: 07 February 2023 Online available: 08 February 2023 Abstract (631) HTML (23) PDF (1176KB)(705) Knowledge map Rylene diimides (RDIs) derivatives are an important class of functional organic dyes. With unique electron-defi- cient conjugated backbones and excellent photoelectronic properties, these polycyclic aromatic hydrocarbons have wide applications in organic field effect transistors, organic photovoltaic devices, and biomedical sensing. Precise modification of the RDIs skeletons can not only regulate molecular energy levels, but also facilitate controllable assembly between π-molecules, which is an effective means to create new π-molecular materials. In the early stage, due to the limitation of synthetic methods, only modifications on the bay positions of RDIs can be achieved. However, the introduction of substituents on these sites would distort the π-plane of RDIs and was not conducive to effective π-stacking between molecules. The selective modifications of RDIs skeletons on the ortho positions do not affect the planarity of the skeletons, which have received much attention in recent years, leading to a series of efficient strategies toward ortho-functionalized RDIs. The methods of ortho-C—H bond functionalization of RDIs such as perylene diimides and naphthalene diimides, and the influence of ortho- modification on the photoelectronic properties and assembly of RDIs derivatives are summarized. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Ir(III)-Catalyzed Novel Three-Component Cascade Trifluoroethoxylation and One-Pot Method to Construct Complex Amide Compounds Chengfu Zeng, Yuan He, Qing Li, Lin Dong Chinese Journal of Organic Chemistry 2023, 43 (3): 1115-1123. DOI: 10.6023/cjoc202210033 Published: 07 February 2023 Online available: 08 February 2023 Abstract (346) HTML (11) PDF (473KB)(348) Knowledge map Ir(III)-catalyzed three-component cascade reaction to construct unique trifluoroethoxylation amide compounds has been developed, meanwhile the fluorinated compounds could continue to react with alcohols to prepare complex spiro isoindolinone derivatives in one-pot. The highly efficient approaches produce various amide compounds by condition- controlled. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Advances in Catalytic Asymmetric Reactions Involving o-Hydroxybenzyl Alcohols Haiqing Wang, Shuang Yang, Yuchen Zhang, Feng Shi Chinese Journal of Organic Chemistry 2023, 43 (3): 974-999. DOI: 10.6023/cjoc202211022 Published: 07 February 2023 Online available: 08 February 2023 Abstract (1287) HTML (63) PDF (1236KB)(1562) Knowledge map Ortho-quinone methides (o-QMs) belong to a class of highly reactive organic intermediates, which play an important role in catalytic asymmetric formations of carbon-carbon bond and carbon-heteroatom bond. However, o-QMs are highly unstable, which led to the underdevelopment of catalytic asymmetric reactions involving o-QMs. The utilization of some precursors for in situ generating o-QMs is a solution to address this challenging issue. Therefore, the development of catalytic asymmetric reactions involving in situ generated o-QMs has absorbed great attention from the chemists. The key to develop such reactions is to exploit easily available and stable precursors of o-QMs. Ortho-hydroxybenzyl alcohols are a kind of o-QM precursors with unique advantages. Hence, the catalytic asymmetric [4+n] cycloadditions, tandem cyclizations and nucleophilic additions of o-hydroxybenzyl alcohols have developed very rapidly in recent years, which have become efficient strategies for the synthesis of chiral oxygen-containing heterocycles and arylmethane derivatives. The catalytic asymmetric reactions involving o-hydroxybenzyl alcohols are summarized, which will open a new window for the design of new type of o-hydroxybenzyl alcohols and their involved catalytic asymmetric reactions. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Synthesis and Characterization of Zinc, Lithium and Magnesium Complexes Containing Pyrrolyl Ligands, and Utilization as Catalysts in Borylation of Aryl Iodides and Hydroboration of Aldehydes and Ketones Yan Dang, Chaohong Jia, Yalan Wang, Li Wang, Yafei Li, Yahong Li Chinese Journal of Organic Chemistry 2023, 43 (3): 1124-1135. DOI: 10.6023/cjoc202211038 Published: 07 February 2023 Online available: 08 February 2023 Abstract (370) HTML (19) PDF (1815KB)(532) Knowledge map The reactions of ZnEt2 with two pyrrolyl ligands 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1- yl)-N,N-dimethylethan-1-amine (HL1) and N-((1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)methanimine (H2L2) generated a zinc ethyl compound [Zn(L1)Et] (1) and a dinuclear complex [Zn2(L2)2(THF)2] (2). The complexes were characterized by 1H NMR, 13C NMR, elemental analysis, and single-crystal X-ray diffraction. Complexes 1 and 2 were employed as catalysts for the borylation of aryl iodides with B2Pin2 (B2Pin2=4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane)). They were both active for this coupling reaction. Complex 1 displays higher activity than that of 2. This borylation transformation promoted by 1 features mild condition, wide substrate scope and high functional group compatibility. Moreover, the catalytic activities of two known compounds previously reported by our group, namely, [Li2(L1)2] (3) and [Mg(L1)2(THF)2] (4), toward borylation of aryl iodides with B2Pin2 were also explored. They cannot catalyze this coupling reaction. Nevertheless, complexes 3 and 4 were catalytically active toward hydroboration of aldehydes and ketones by pinacolborane (HBpin), giving a variety of borate esters in excellent yields in a very short time. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Progress on the Synthesis and Activity of Cyclic Dinucleotides as Stimulator of Interferon Gene (STING) Agonists Tianyang Wang, Yan-Mei Li Chinese Journal of Organic Chemistry 2023, 43 (3): 892-913. DOI: 10.6023/cjoc202211049 Published: 23 February 2023 Abstract (658) HTML (43) PDF (883KB)(817) Knowledge map Cyclic dinucleotide is the agonist of cyclic guanosine-adenosine synthase-stimulator of interferon genes (cGAS- STING) innate immune signal pathway. At present, four kinds of natural STING cyclic dinucleotide agonists have been discovered. In recent years, with the revelation of the mechanism of cGAS-STING pathway, the activation of STING pathway for immunotherapy has become a hot topic. The modification of cyclic dinucleotides to improve their drug activities and properties has become an important means to promote their application in clinical treatment. Here, the important progress in the synthesis and activity of cyclic dinucleotides as STING agonists in recent years is reviewed. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Haloperfluoroalkylation of Unactivated Terminal Alkenes over Phenylphenothiazine-Based Porous Organic Polymers Rui Wang, Lang Gao, Cen Zhou, Xiao Zhang Chinese Journal of Organic Chemistry 2023, 43 (3): 1136-1145. DOI: 10.6023/cjoc202211013 Published: 18 January 2023 Abstract (850) HTML (45) PDF (1624KB)(752) Knowledge map Photocatalytic heterogeneous chlorotrifluoromethylation and iodoperfluoroalkylation of unactivated terminal alkenes have been achieved under the catalysis of phenylphenothiazine-based porous organic polymer (PTH-POP). This method offers a transition-metal-free and recyclable platform to access valuable perfluoroalkylated compounds in a highly efficient fashion. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS α-Acylation of Olefins via Photocatalysis Hongyu Hou, Yuanyuan Cheng, Bin Chen, Chenho Tung, Lizhu Wu Chinese Journal of Organic Chemistry 2023, 43 (3): 1012-1022. DOI: 10.6023/cjoc202211048 Published: 18 January 2023 Abstract (768) HTML (34) PDF (787KB)(1181) Knowledge map The cheap and readily available olefin substrates have received much attention for the synthesis of structurally rich and high value-added ketones, aldehydes, carboxylic acids and their derivatives via α-acylation. Multicomponent tandem α-acylation of olefins achieves high efficiency and selectivity by N-heterocyclic carbene or transition metal catalysis, albeit with narrow reaction modes and substrates. Rapid growth of photocatalysis in organic transformation has introduced new methodologies to undergo the α-acylation of olefins with broad substrate scope. The research progress and prospect for the future development in this active research field is highlighted. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Recent Advances in Nickel Catalyzed Asymmetric Acylation Reactions Yanyan Zhang, Zhuzhu Zhang, Shengqing Zhu, Lingling Chu Chinese Journal of Organic Chemistry 2023, 43 (3): 1023-1035. DOI: 10.6023/cjoc202211032 Published: 12 January 2023 Abstract (1263) HTML (49) PDF (735KB)(1482) Knowledge map Chiral αα-carbonyl compounds are important structural units in natural products and pharmaceuticals and versatile synthetic building blocks in organic synthesis. Transition metal-catalyzed asymmetric acylation reaction is one of the most straightforward methods for preparing these compounds. In particular, significant progress has been made in the area of nickel-catalyzed asymmetric acylation reaction, due to the unique properties of nickel catalysts. The latest progress of nickel-catalyzed asymmetric acylation reaction, including nickel-catalyzed asymmetric alkyl-acyl cross-coupling reaction, asymmetric hydroacylation of alkene and asymmetric acyl-functionalization alkene, is summarized. Fig. & Tab. | Reference | Related Articles | Metrics REVIEWS Recent Advances in Ionic Transfer Reactions Luomo Li, Xiaohui Yang Chinese Journal of Organic Chemistry 2023, 43 (3): 1036-1044. DOI: 10.6023/cjoc202211047 Published: 12 January 2023 Abstract (3267) HTML (33) PDF (626KB)(805) Knowledge map In recent years, a series of novel organic reactions, named “ionic transfer reaction”, has received much attention. This kind of reaction has a characteristic mechanism and avoids the use of inflammable, explosive, highly toxic and other difficult to operate reagents. It provides a new powerful tool for transfer functionalizations of unsaturated compounds, such as transfer hydrosilylations, transfer hydrogenations, transfer hydrohalogenations, and transfer hydrocyanations. Herein, the recent progress of ionic transfer reactions and related mechanisms are summarized. Furthermore, the future developments of ionic transfer reactions are prospected. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Recent Advances in Transition Metal-Catalyzed B—H Bond Activation for Synthesis of o-Carborane Derivatives with B—Heteroatom Bond Hairui Jia, Zaozao Qiu Chinese Journal of Organic Chemistry 2023, 43 (3): 1045-1068. DOI: 10.6023/cjoc202211040 Published: 05 January 2023 Abstract (487) HTML (29) PDF (3417KB)(660) Knowledge map Carboranes are a class of carbon-boron molecular clusters with exceptional thermal and chemical stabilities. They are finding a variety of applications in medicine, materials, and coordination/organometallic chemistry as functional building blocks. Recently, transition metal catalyzed regioselective o-carborane B—H activation has been rapidly developed, offering a series of novel methodologies for selective cage boron functionalization. The current state of functionalization of o-carboranes to form B—B, B—N, B—O, B—S, and B—halogen bonds using transition metal-catalyzed B—H activation strategy is summarized. Some reaction mechanisms are highlighted, and the future challenges and focus of the carborane B—heteroatom bond construction are discussed. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines Hua Huang, Xin Li, Jianke Su, Qiuling Song Chinese Journal of Organic Chemistry 2023, 43 (3): 1146-1156. DOI: 10.6023/cjoc202210031 Published: 21 December 2022 Abstract (424) HTML (8) PDF (587KB)(537) Knowledge map A novel transition-metal-free protocol for the synthesis of 1-alkyl-3-(2-oxo-2-aryl/alkyl-ethyl)indolin-2-ones is developed. This work reveals that oxoindole skeletons can be directly constructed from ortho-vinylanilines and commercially available halogenated difluoroalkyl reagents via a C—N cleavage/new C—N bonds and C—C bond formation cascade. This reaction portrays high efficiency and excellent functional group compatibility, and has great potential in the late-stage modifications of pharmaceutical molecules and natural products. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics REVIEWS Recent Advances of the Atherton-Todd Reaction Siqiang Fang, Zanjiao Liu, Tianli Wang Chinese Journal of Organic Chemistry 2023, 43 (3): 1069-1083. DOI: 10.6023/cjoc202210032 Published: 21 December 2022 Abstract (843) HTML (40) PDF (873KB)(1708) Knowledge map Phosphoramides or phosphates and their derivatives are a very important class of phosphorus-containing organic molecules, which are widely applied in medicinal chemistry, material chemistry and organic catalysis. As one of the most effective methods towards constructing phosphorus compounds, the Atherton-Todd reaction involves in situ halogenation of P(O)-H molecules with tetrachloromethane to generate the key intermediates of phosphoryl chlorides in the presence of bases, which subsequently react with amines or alcohols to form the corresponding phosphoramide or phosphate products. In recent years, this reaction has been widely explored by synthetic chemists due to its ease of operation, high atom economy, broad substrate versatility, and ease of incorporation of phosphorus units into active structural fragments. The research progress of the Atherton-Todd reaction and its application in organic synthesis in recent decades are summarized, and a brief outlook on the current research challenges is put forward, hoping to provide reference and thinking for the further development of the Atherton-Todd reaction. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES High Regioselective Synthesis of N2-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid Jian Ji, Jinhua Liu, Cong Guan, Xuwen Chen, Yun Zhao, Shunying Liu Chinese Journal of Organic Chemistry 2023, 43 (3): 1168-1176. DOI: 10.6023/cjoc202209021 Published: 14 December 2022 Abstract (419) HTML (15) PDF (686KB)(472) Knowledge map The green and highly efficient synthesis of N2-substituted 1,2,3-triazoles remains challenging due to the lower electron density at the N2-atom than that at two terminal nitrogen atoms (N1 and N3) of the triazole heterocycle. Cheap and easily available alcohols were developed as starting points to couple with N-sulfonyl-1,2,3-triazole instead of halogenated reagents catalyzed by in-situ generated sulfonic acid. The resulting products, N2-substituted 1,2,3-triazoles, were obtained with high regioselectivity and in good yields (68%~83%) without any additional catalysts or additives. The reaction has a broad substrate adaptability and functional group compatibility, including aryl benzyl and alkyl alcohols. Preliminary mechanistic studies indicate that methanesulfonic acid (MsOH) which in situ produced by the hydrolysis of N-sulfonyl-1,2,3-triazoles promoted the reaction, and high regioselectivity was promoted through the thermally stable intermediate N2H-1,2,3-triazole. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics ARTICLES Photocatalyzed 2∶2 Coupling of Styrene and BrCF2CO2Me: A Facile Synthesis of Bis-difluoroacetylated Hexestrol Derivatives Shenhao Chen, Song Zou, Chanjuan Xi Chinese Journal of Organic Chemistry 2023, 43 (3): 1157-1167. DOI: 10.6023/cjoc202210009 Published: 14 December 2022 Abstract (539) HTML (15) PDF (875KB)(454) Knowledge map Photoredox-catalyzed 2∶2 coupling of styrene and BrCF2CO2Me is reported, which undergoes a homo-coupling of in situ generated β-CF2CO2Me substituted benzyl radical. The reaction features a wide substrate scope and functional group tolerance to afford bis-difluoroacetylated hexestrol derivatives with high yields. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics ARTICLES Green Method for Constructing Phthalides via Oxidative Coupling of Aromatic Acids and Acrylates in Neat Water and Air Wenting Wei, Zhuangzhuang Li, Wandi Li, Jiaqi Li, Xianying Shi Chinese Journal of Organic Chemistry 2023, 43 (3): 1177-1186. DOI: 10.6023/cjoc202208034 Published: 08 November 2022 Abstract (489) HTML (22) PDF (517KB)(452) Knowledge map Phthalides represent an important class of bioactive heterocycle extensively found in pharmaceuticals and natural products, their syntheses have attracted extensively attention. A water-promoted and rhodium-catalyzed [3+2] tandem cyclization of aromatic acids and acrylates has been developed in air and neat water free of any additives, which provides an environmentally benign approach for constructing phthalide motifs. Compared with previous literatures, this methodology features quite simple reaction conditions, simple operation and additive-free. Mechanistic studies indicate that apart from the many other well-known oxidations of Rh(I) by external oxidant, hydrogen transfer with the acrylate being a hydrogen acceptor is involved to regenerate the active Rh species, which is different from documented metal-catalyzed phthalides syntheses. The application of this protocol is further demonstrated by the green synthesis of biologically active isoochracinic acid in one step. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics ARTICLES Rhodium-Catalyzed Tandem Acylmethylation/Annulation Reactions of 2-Aryl-2H-indazoles with Sulfoxonium Ylides: Easy Access to 6-Arylindazolo[2,3-a]quinolines Zhen Tang, Chao Pi, Yangjie Wu, Xiuling Cui Chinese Journal of Organic Chemistry 2023, 43 (3): 1187-1196. DOI: 10.6023/cjoc202206052 Published: 15 September 2022 Online available: 15 September 2022 Abstract (498) HTML (14) PDF (654KB)(442) Knowledge map An efficient synthesis of 6-arylindazolo[2,3-a]quinolines starting from 2-aryl-2H-indazoles with sulfoxonium ylides via rhodium(III)-catalyzed C—H activation and cyclization reaction has been described. This transformation features high efficiency, tolerates various functional groups, avoids external oxidant and produces dimethyl sulfoxide (DMSO) and H2O as the sole by-products. In addition, the scale-up reaction demonstrated the practicability of this protocol in industry. Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics