Default Latest Most Read Please wait a minute... Reviews Recent Progress on Difluoromethylation Methods Wang Weiqiang, Yu Qinwei, Zhang Qian, Li Jiangwei, Hui Feng, Yang Jianming, Lü Jian Chin. J. Org. Chem. 2018, 38 (7): 1569-1585. DOI: 10.6023/cjoc201801041 Published: 27 April 2018 Abstract (1665) PDF (879KB)(2780) Knowledge map The difluoromethyl functional group (CF2H) which has strong lipophilic and electron-withdrawing properties can significantly enhance the physiological activity of organic molecules. The applications of CF2H-containing compounds in the fields of drugs, agrochemicals and so on have attracted great attention of many research groups. Therefore, the development of effective and general methodologies for the selective incorporation of difluoromethyl groups has become one of the hotspots in the field of organic chemistry. Recently, new difluoromethylation reagents and methods that were able to efficiently incorporate the difluoromethyl group under mild conditions have been developed rapidly, that pave the way for the facile introduction of difluoromethyl group into site-specific positions of the target molecules. In this paper, we will first briefly introduce some organic molecules with different functional groups which can be difluoromethylated, and then focus on the development of the recent high-performance difluoromethylation reagents, new reactions and catalysts. Finally, we will discuss the remaining problems and challenges in this particular field. Reference | Related Articles | Metrics Cited: CSCD(2) Reviews Recent Advances of Phosphorus-Centered Radical Promoted Difunctionalization of Unsaturated Carbon-Carbon Bonds Gao Yuzhen, Tang Guo, Zhao Yufen Chin. J. Org. Chem. 2018, 38 (1): 62-74. DOI: 10.6023/cjoc201708023 Published: 08 September 2017 Abstract (1512) PDF (839KB)(2426) Knowledge map The scientists have been working on developing more efficient and green ways to synthesize organophosphorus compounds as they have broad utilities such as reagents for chemical reactions, photovoltaic materials, flame retardants, biologically active molecules and so on. The difunctionalization reactions between P-center radicals and unsaturated compounds provide powerful methods for the synthesis of organophosphorus compounds in least and concise steps. This review will summarize the recent development in this area on the basis of different types of P-centered radical initiators. Reference | Related Articles | Metrics Cited: CSCD(1) Iron-Catalyzed Deoxygenative Diborylation of Ketones to Internal gem-Diboronates He Zeyu, Fan Min, Xu Jia'neng, Hu Yue, Wang Lu, Wu Xudong, Xia Chungu, Liu Chao Chinese Journal of Organic Chemistry 2019, 39 (12): 3438-3445. DOI: 10.6023/cjoc201909008 Published: 25 September 2019 Abstract (1482) PDF (491KB)(1165) Knowledge map An iron catalyzed deoxygenative diborylation of ketones to access a variety of internal gem-diboronates has been developed. A scale-up synthesis of such gem-diboronates is also applicable under this condition. Meanwhile, common organic solvent acetone was used as start material to synthesize corresponding internal gem-diboronate, and further mono- or di-functionalization of such internal gem-diboronate has also been explored to demonstrate the synthetic potential of internal gem-diboronates. Reference | Supporting Info. | Related Articles | Metrics Articles Carbazolation Study of Active Arenes with Carbazole-Containing Hypervalent Iodine(III) Reagents Lan Tianlei, Zhang Yue, Liu Wei, Xi Chanjuan, Chen Chao Chinese Journal of Organic Chemistry 2019, 39 (8): 2166-2174. DOI: 10.6023/cjoc201905050 Published: 17 July 2019 Abstract (1456) PDF (562KB)(1773) Knowledge map Carbazole and its derivatives are widely used in the field of medicine and photoelectric materials. A kind of stable cyclic hypervalent iodine reagents containing carbazole group was developed, which belong to benziodoxole compounds. In the presence of Cu(I) catalyst, these reagents reacted with aromatic substrates to give N-aryl carbazole derivatives. The reaction conditions are mild and suitable for a variety of electron-rich arenes. And a radical mechanism was proposed. Reference | Supporting Info. | Related Articles | Metrics Reviews Progress of Trifluoromethylation Using Trifluoroacetic Acid and Its Derivatives as CF3-Sources Ji Xiaoming, Shi Guangfa, Zhang Yanghui Chin. J. Org. Chem. 2019, 39 (4): 929-939. DOI: 10.6023/cjoc201810033 Published: 21 December 2018 Abstract (1365) PDF (752KB)(2265) Knowledge map Organic molecules containing trifluoromethyl groups often exhibit unique physical and chemical properties, and have found extensive applications. Trifluoroacetic acid and its derivatives have advantages including low cost, ready availability and high stability. Furthermore, CO2 is the byproduct. Therefore, trifluoroacetic acid and its derivatives are ideal trifluoromethylating reagents, and have great application potentials. The progress of trifluoromethylation reactions using trifluoroacetic acid and its derivatives as CF3-sources is reviewed, including the reactions of C-X (X=Br and I), C-H, and C=X (X=C, O). The mechanisms are also introduced. Reference | Related Articles | Metrics REVIEW Progress of Difluoromethyl Heteroaryl Sulfones as Difluoroalkylation Reagents Tao Xuefen, Sheng Rong, Bao Kun, Wang Yuxin, Jin Yinxiu Chinese Journal of Organic Chemistry 2019, 39 (10): 2726-2734. DOI: 10.6023/cjoc201903063 Published: 12 June 2019 Abstract (1355) HTML (28) PDF (722KB)(1355) Knowledge map Due to the uniqueness of fluorine atom and C—F bond, difluoromethylene has special properties. As a bioisostere of an oxygen or a carbonyl group, it plays an important role in medicines, pesticides and materials. Difluoromethyl heteroaryl sulfones, represented by 2-PySO2CF2H (Hu reagent), have been developed recently as difluoromethylation reagents, and widely recognized by synthetic chemists for their ease of preparation, good functional group tolerance and universal applicability to a wide range of carbonyl compounds. Through different types of reactions such as nucleophilic substitution, nucleophilic addition, Julia-Kocienski olefination reaction, and radical-mediated difunctionalization, they introduced difluoromethyl, difluoromethylene, gem-difluoroalkene and other fluorine-containing groups into aldehydes, ketones, and heterocyclic compounds. For the first time, the synthesis of fluorine-containing organic compounds involved in various difluoromethyl heteroaryl sulfones in the past decade is reviewed from the perspective of reaction types and their application studies. Fig. & Tab. | Reference | Related Articles | Metrics Articles Cobalt-Catalyzed Dehydrogenative Silylation of Vinylarenes Cheng Biao, Lu Peng, Zhao Jiajin, Lu Zhan Chin. J. Org. Chem. 2019, 39 (6): 1704-1710. DOI: 10.6023/cjoc201903018 Published: 16 April 2019 Abstract (1303) PDF (1197KB)(1069) Knowledge map A highly chemo-, regio-, and stereo-selective cobalt-catalyzed dehydrogenative silylation of vinylarenes was described. The imidazoline iminopyridine cobalt complex could promote this reaction effectively and improve the chemoselectivity dramatically. This protocol used earth-abundant transition metal, readily available alkenes and hydrosilanes to construct valuable vinylsilanes. The reaction could be carried out in gramscale and the proposed mechanism was also described. Reference | Supporting Info. | Related Articles | Metrics Reviews Recent Advances in Organic Electrochemical Synthesis and Application of Hypervalent Iodine Reagents Zhang Huaiyuan, Tang Rongping, Shi Xingli, Xie Lin, Wu Jiawei Chin. J. Org. Chem. 2019, 39 (7): 1837-1845. DOI: 10.6023/cjoc201902006 Published: 09 April 2019 Abstract (1281) PDF (714KB)(2010) Knowledge map Anodic oxidation of aryl iodine compouds is a green and efficient method for the synthesis of hypervalent iodine reagents. This method replaces chemical reagents with electric current, avoiding the use of expensive and handle difficult oxidants such as m-CPBA, H2O2, oxone, selectfluor etc. Electrochemically generated hypervalent iodine reagents can not only promote fluorination, oxidative cyclization, but also be successfully applied in the total synthesis of natural products. In addition, recyclable aryl iodine mediator can be used to indirect anodic fluorination and easily separated from products. The organic electrochemical synthesis of hypervalent iodine reagents and their applications in various chemical transformations are reviewed. Reference | Related Articles | Metrics Reviews Progress in Activation of Small Molecules Promoted by Frustrated Lewis Pairs Zhang Zhenbei, Sun Wei, Cao Zhishan Chin. J. Org. Chem. 2018, 38 (6): 1292-1318. DOI: 10.6023/cjoc201801003 Published: 08 March 2018 Abstract (1271) PDF (1322KB)(2385) Knowledge map Frustrated Lewis pairs (FLPs) chemistry has grown rapidly during the last decade and provided a new strategy for the activation of a variety of small molecules, such as hydrogen, olefins, alkynes, carbon dioxide, tetrahydrofuran and hydrosilane etc. The activations of these molecules have probided a new method in the utility of main group element. The structure and reactivity of FLPs are reviewed and the recent progress in activation of small molecules promoted by frustrated Lewis pairs is introduced. Reference | Related Articles | Metrics Reviews Recent Advance in Transition-Metal-Catalyzed Silylation of C-H Bonds Huang Hongtai, Li Tao, Wang Jiazhuang, Qin Guiping, Xiao Tiebo Chin. J. Org. Chem. 2019, 39 (6): 1511-1521. DOI: 10.6023/cjoc201903078 Published: 28 May 2019 Abstract (1247) PDF (1536KB)(1833) Knowledge map Organosilicon compounds play an important role in pharmaceutical chemistry, material science and organic synthesis. Transition-metal-catalyzed direct silylation of C-H bond, as one of the most concise and efficient methods for the synthesis of organosilanes, has developed rapidly in recent years. In this paper, the recent advance in transition-metal-catalyzed silylation of C-H bonds since 2015 is mainly reviewed. Reference | Related Articles | Metrics Cross-Coupling of C-Si Bond by Using Silyl Reagents Wang Mingfeng, Yu Maodong, Wang Wenshu, Lin Weili, Luo Feixian Chinese Journal of Organic Chemistry 2019, 39 (11): 3145-3153. DOI: 10.6023/cjoc201904024 Published: 24 June 2019 Abstract (1230) HTML (49) PDF (596KB)(2122) Knowledge map Organosilanes have been widely applied in synthetic chemistry, pharmaceuticals, agrochemicals, and materials due to the special properties. Several synthetic strategies including nucleophilic substitution, hydrosilylation of alkene, and C-H silylation have been developed. In recent years, significant progress has advanced in the cross-coupling of C-Si bond for the synthesis of organosilanes, especially in the break-through of the cross-coupling of C(sp3)-Si bond. It has become one of the hottest issues in synthetic chemistry. The recent progress on the cross-coupling of C-Si bond by using silyl reagents is summarized. The application of silyl reagents in cross-coupling for C-Si bond formation including silyl boranes, organosilyl magnesium, organosilyl zinc, unasymetric disilanes, organosilyl aluminum and organosilyl lithium reagents is mainly discussed. Fig. & Tab. | Reference | Related Articles | Metrics Articles Phosphine-Mediated Sequential Staudinger/Aza-Michael Addition of Azides with Unsaturated Ketones to Synthesize β-Amino Substituted Ketones Cong Tiantian, Wang Huamin, Liu Yuanyuan, Wu Haihong, Zhang Junliang Chinese Journal of Organic Chemistry 2019, 39 (8): 2157-2165. DOI: 10.6023/cjoc201906005 Published: 17 July 2019 Abstract (1203) PDF (624KB)(1399) Knowledge map A phosphine-mediated Staudinger/Aza-Michael addition of azides with trifluoromethyl substituted α,β-unsaturated ketones was developed, giving hydroamination products in medium to good yields (up to 96%). The hydroamination products could be prepared on gram scale and a wide range of substrates are tolerated under the optimized reaction conditions (30 examples). 31P NMR experiments indicate that this reaction was initiated by Staudinger reaction of azide with phosphine. Reference | Supporting Info. | Related Articles | Metrics Articles Nickel-Catalyzed Difluoromethylation of (Hetero)aryl Bromides with BrCF2H Gao Xing, He Xu, Zhang Xingang Chin. J. Org. Chem. 2019, 39 (1): 215-222. DOI: 10.6023/cjoc201808014 Published: 12 October 2018 Abstract (1148) PDF (490KB)(1491) Knowledge map A nickel-catalyzed direct difluoromethylation of (hetero)aryl bromides with bromodifluoromethane (BrCF2H) is described. This reaction features high efficiency, broad substrate scope and high functional group tolerance, providing a cost-efficient and straightforward route for applications in medicinal chemistry. Preliminary mechanistic studies reveal that a nickel-based, reductive cross-coupling catalytic cycle is involved in the reaction. Reference | Supporting Info. | Related Articles | Metrics Reviews Progress of Fluorescent Bio-probe Based on Water-Soluble Boron-dipyrromethene Lu Bowei, Meng Shuxian, Feng Yaqing Chin. J. Org. Chem. 2018, 38 (2): 350-362. DOI: 10.6023/cjoc201706018 Published: 11 October 2017 Abstract (1132) PDF (829KB)(1631) Knowledge map Recently, the fluorescent bio-probe based on water-soluble boron-dipyrromethene (BODIPY) obtains enormous progress on structural optimization and functional modification, and becomes novel high-performance biological imaging materials owing to the development of hydrophilic modification. Focusing on the methods for improving the hydrophilicity of BODIPY, the water-soluble BODIPYs have been classified as ionic probe, electrically-neutral probe and amphiphilic probe. The research progress on the application of water-soluble BODIPY dyes in field of biology and medicine since 2006 has been summarized in this review, such as detection of necessary and pathogenicbiological chemical components, early detection and intervention of cancer, labelling drug delivery, marking specific organelles, real-time monitoring of biochemical and property changes with cells, andphotodynamic therapy. The merits of methods for improving the hydrophilicity and main issues of current studies have been summed up. The hypothesis for future directions has also been put forward. Reference | Related Articles | Metrics Cited: CSCD(1) Reviews Research Progress towards Synthesis of Aryl Boronic Acid Compounds Xu Yuliang, Fang Hao Chin. J. Org. Chem. 2018, 38 (4): 738-751. DOI: 10.6023/cjoc201709045 Published: 05 December 2017 Abstract (1081) PDF (846KB)(2186) Knowledge map Aromatic boronic acids and esters are essential intermediates and have been widely used in biology, medicine and material science. In this paper, the resent progress on their synthesis is summarized, especially Pd-catalyzed borylation of aryl chlorides with steric hindrance substrates, other metal (Ni, Cu, Fe, Zn, Rh, Co)-catalyzed borylation, metal-free borylation, and photoinduced borylation. Reference | Related Articles | Metrics Reviews Recent Advances in Transition Metal-Promoted Trifluoromethylation Reactions Chen Donghan, Yang Wen, Yao Yongqi, Yang Xin, Deng Yingying, Yang Dingqiao Chin. J. Org. Chem. 2018, 38 (10): 2571-2589. DOI: 10.6023/cjoc201803045 Published: 06 June 2018 Abstract (1016) PDF (956KB)(2744) Knowledge map Recently, transition metal-promoted trifluoromethylation has been developed rapidly. Starting with the types of transition metal that promote the trifluoromethylation reactions, the research progress of trifluoromethylation promoted by silver, iron, palladium, nickel, rhodium and cobalt in recent years is reviewed. Moreover, the possible mechanisms of some parts of reactions are also discussed. Reference | Related Articles | Metrics Articles Phosphine-Catalyzed[3+2] Annulations with γ-Methyl Allenoates Ma Rong, Song Gege, Xi Qiuzhen, Yang Liu, Li Er-Qing, Duan Zheng Chin. J. Org. Chem. 2019, 39 (8): 2196-2202. DOI: 10.6023/cjoc201901040 Published: 09 April 2019 Abstract (998) PDF (508KB)(887) Knowledge map The phosphine-catalyzed[3+2] annulation of γ-methyl allenoates with 2-arylidene-1H-indene-1,3(2H)-diones is reported. In the reaction, a series of highly functionalized spiro[4.4]dec-6-ene skeletons were obtained in moderate to good yields and high diastereoselectivities. It should be noted that the perfect α-regioselective annulation adducts were obtained with simple PPh3 catalyst. Reference | Supporting Info. | Related Articles | Metrics Reviews Research Progress of Asymmetric Synthesis of Optically Active P-Stereogenic Organophosphoryl Compounds by Chiral Induction Liu Shuang, Li Yuming, Wang Dian, Wei Rong, Miao Zhiwei Chin. J. Org. Chem. 2018, 38 (2): 341-349. DOI: 10.6023/cjoc201708040 Published: 16 October 2017 Abstract (992) PDF (594KB)(1756) Knowledge map Organo-phosphorus chemistry is an important branch of organic chemistry and life science research. P-Stereogenic organophosphorus compounds have attracted great interest due to their potential applications in the fields of pharmaceutical chemistry, agrochemistry, material science and as ligands for asymmetric catalysis. The preparation of enantiomerically enriched phosphorus compounds with P-stereogenic centers using natural chiral compounds as chiral auxiliary has received considerable attention. The recent development of the asymmetric synthesis of P-stereogenic organophosphoryl compounds employing menthol, sparteine, ephedrine, and carbohydrates as chiral auxiliary is summarized. Reference | Related Articles | Metrics Cited: CSCD(1) Notes NaBH4/I2-Mediated Efficient Iodination of Alcohols Fan Zhengning, Zhang Bo, Xi Chanjuan Chin. J. Org. Chem. 2019, 39 (8): 2333-2337. DOI: 10.6023/cjoc201903036 Published: 26 April 2019 Abstract (982) PDF (496KB)(908) Knowledge map A simple, mild, and high yielding procedure for the iodination of alcohols using a combination of NaBH4 and I2 is described. The effectiveness of the protocol is achieved with benzylic alcohols and primary alkylic alcohols whereas allylic and secondary alcohols are found to be unreactive. Reference | Supporting Info. | Related Articles | Metrics Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones Wang Qiaotian, Han Caifang, Feng Xiangqing, Du Haifeng Chin. J. Org. Chem. 2019, 39 (8): 2257-2263. DOI: 10.6023/cjoc201903076 Published: 10 May 2019 Abstract (941) PDF (552KB)(1137) Knowledge map The chemistry of frustrated Lewis pairs (FLPs) is among the challenging frontiers of synthetic chemistry, which provides a powerful approach for metal-free catalytic hyrogenations and Piers-type hydrosilylations. In recent years, a significant progress has been made in this field. However, the deveopment of asymmetric reactions is still sluggish. The lacks of highly effective and enantioselective chiral FLP catalysts represent the key issue. C2-symmetric 1,1'-spirobiindane is one privileged framework in chiral ligands and catalysts. On the basis of chiral binaphthyl diene-derived frustrated Lewis pairs (FLPs) developed by our group, in this work, we designed and synthesized a novel class of chiral spiro dienes, which could further react with Piers' borane via the hydroboration reaction to generate chiral boranes in situ. With the combination of chiral borane and tri-tert-butylphosphine as an FLP catalyst, an asymmetric Piers-type hydrosilylation of simple ketones was successfully realized to give the desired secondary alcohols with up to 90% ee. Reference | Supporting Info. | Related Articles | Metrics Reviews Recent Advances in Alkaline-Earth-Metal-Catalyzed Hydrofunctionalization Reactions Li Yuanyuan, Cheng Yuhua, Shan Chunhui, Zhang Jing, Xu Dongdong, Bai Ruopeng, Qu Lingbo, Lan Yu Chin. J. Org. Chem. 2018, 38 (8): 1885-1896. DOI: 10.6023/cjoc201804031 Published: 17 May 2018 Abstract (937) PDF (780KB)(1394) Knowledge map Alkaline-earth-metal compounds have been widely concerned due to its abundant reserve and the low-cost. In recent years, alkaline-earth-metal catalysis has achieved great progress in dehydrocoupling, hydroboration, hydrophosphination, hydroamination, hydrosilylation reactions experimentally and therotically. These types of reaction and catalytic mechanism, leading to indentify the role of alkaline-earth-metal in hydrogenation and dehydrogenation reaction are summarized. These reactions, in which the metal-hydride act as active species, generally undergo the reaction pathway involving the cleavage and formation of the metal-hydride covalent bond. The reaction features and mechanisms are generally recognized accrossing to the classification and discussion of these reactions, which would provide guidance for further development of alkaline-earth-metal catalysis. Reference | Related Articles | Metrics Cited: CSCD(2) Reviews Advances Research in Synthesis of Aza-heterocyclic Compounds Involving Vinyl Azides Wang Yuying, Liu Li, Wang Yeming Chin. J. Org. Chem. 2018, 38 (5): 1009-1028. DOI: 10.6023/cjoc201711043 Published: 10 January 2018 Abstract (922) PDF (1134KB)(1427) Knowledge map Vinyl azides have been extensively studied in organic synthesis since 1910. As a series of important intermediates, vinyl azides have a wide range of applications in recent years, especially in the synthesis of heterocyclic compounds catalyzed by transition-metals. The progress of the construction of aza-heterocyclic compounds in the field of organic synthesis is reviewed. Reference | Related Articles | Metrics Cited: CSCD(1) Reviews Recent Advances of α-Aryl Vinyl Azides in Nitrogen Heterocycle Synthesis Yan Jun, Ji Xiaoyue, Hua Shugui, Wang Jing Chin. J. Org. Chem. 2018, 38 (4): 791-801. DOI: 10.6023/cjoc201709025 Published: 15 November 2017 Abstract (899) PDF (599KB)(1433) Knowledge map Nitrogen heterocyclic compounds can be found in various natural products, pharmaceutical chemistry and material chemistry. Due to azide group linked to olefins, α-aryl vinyl azide has unique properties, which can act as electrophilic reagents, nucleophilic reagent, or radical acceptor. Diverse reaction pathways of α-aryl vinyl azide provide great opportunities to generate highly reactive intermediates with unusual or unconventional reactivities, making it possible to develop novel reaction. Recently, more and more synthetic chemists used α-aryl vinyl azide as a key three atoms synthon for the construction of diverse structurally complex N-heterocyclic compounds. This review will introduce systematically the reactivities of α-aryl vinyl azide and the developments of the recent application of α-aryl vinyl azide in nitrogen heterocycle synthesis, including mechanism, reaction characteristics and application study, thus it may be helpful for the research on nitrogen heterocycle synthesis. Reference | Related Articles | Metrics Articles Phosphine-Catalyzed[4+1] Annulation of Salicyl Imines with Maleimides and Synthesis of Spiro[benzofuran-2,3'-pyrrolidine] Derivatives Yang Mei, Cao Shixuan, He Zhengjie Chin. J. Org. Chem. 2019, 39 (8): 2235-2242. DOI: 10.6023/cjoc201904041 Published: 15 May 2019 Abstract (842) PDF (495KB)(968) Knowledge map In this work, a phosphine-catalyzed[4+1] annulation between salicyl imines and maleimides has been successfully developed, which readily produces spiro[benzofuran-2,3'-pyrrolidine] derivatives in 44%~99% yields. The annulation products were obtained as a pair of syn-and anti-isomers with dr 1.6:1~5:1. The syn-and anti-isomers can be readily separated by column chromatography on silica gel. Thus, this reaction constitutes a simple and efficient method for the synthesis of spiro[benzofuran-2,3'-pyrrolidines]. Presumably, the reaction is initiated by in situ generated non-allylic P-ylide from maleimide and PPh3, and proceeds through a cascade sequence of nucleophilic addition/intramolecular SN2-like substitution. It accordingly represents a new example of the phosphine-catalyzed[4+1] annulation via in situ generated non-allylic P-ylides. Reference | Supporting Info. | Related Articles | Metrics Articles Pentafluoroethyl-Substituted Sulfonium Ylides: New Electrophilic Pentafluoroethylating Reagents Liu Yafei, Ge Hangming, Lu Long, Shen Qilong Chin. J. Org. Chem. 2019, 39 (1): 257-264. DOI: 10.6023/cjoc201807018 Published: 10 September 2018 Abstract (835) PDF (461KB)(720) Knowledge map Two electrophilic pentafluoroethylating reagents of pentafluoroethyl(p-methylphenyl)sulfonium bis(carbometh- oxy)methylide (4a) and pentafluoroethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide (4b), and their reactions under mild conditions with β-ketoesters, aryl iodides and heteroaromatics are described. Reference | Supporting Info. | Related Articles | Metrics Reviews Recent Advances in Oxidative Coupling Reaction Catalyzed by Low-Valence Iodine Yan Yizhe, Cui Chang, Li Zheng Chin. J. Org. Chem. 2018, 38 (10): 2501-2518. DOI: 10.6023/cjoc201805016 Published: 15 June 2018 Abstract (835) PDF (1059KB)(1380) Knowledge map In recent years, low-valence iodine-catalyzed oxidative coupling reaction has made rapid progress, providing an effective method for the construction of C—C, C—O, C—N, C—S, C—P and other chemical bonds. Compared with the transition metal-catalyzed oxidation coupling reaction, this protocol is metal-free under mild conditions. It avoids the high cost and toxicity of transition metal catalyst, which meets the requirements of green chemistry. Therefore, iodine catalysis has attracted much attention of the synthetic chemists. The research progress on low-valence iodine-catalyzed oxidative coupling from 2010 to now is summarized, and outlook of this field is also prospected. Reference | Related Articles | Metrics Cited: CSCD(2) Articles I2/CuI-Mediated Oxidative Cyclization of Enamides to Polysubstituted Oxazoles Yu Wenquan, Chang Junbiao Chin. J. Org. Chem. 2018, 38 (1): 215-220. DOI: 10.6023/cjoc201708009 Published: 15 September 2017 Abstract (814) PDF (485KB)(636) Knowledge map A concise and efficient iodine/copper(I) iodide-mediated intramolecular oxidative C—O bond formation reaction has been developed for oxazole synthesis. Under the optimal reaction conditions, oxidative cyclization of readily accessible enamide substrates provides facile access to a variety of oxazole derivatives bearing aryl, alkyl, amide, ester, and acyl substituents. Reference | Supporting Info. | Related Articles | Metrics Cited: CSCD(2) Reviews Research Progress of Molecular Alkaline-Earth Metal Hydrides Shi Xianghui, Liu Zhizhou, Cheng Jianhua Chin. J. Org. Chem. 2019, 39 (6): 1557-1567. DOI: 10.6023/cjoc201903043 Published: 06 May 2019 Abstract (794) PDF (1525KB)(1123) Knowledge map Alkaline-earth metals continue to receive growing interest, as they are used as low-cost and non-toxic alternatives to transition-metals in various organic transformations. As ionic character and bond lengths increase along the row in the order Mg2+2+2+2+, bond energies decrease along the same row, the corresponding metal hydrides are apt to the formation of insoluble metal hydrides[AeH2]∞ (Ae=Mg, Ca, Sr, Ba) through Schlenk equilibrium in solution. Recently, a series of alkaline-earth metal hydrides stabilized by suitable ligands were discovered and characterized, and stoichiometric and catalytic reactions with small molecules were studied as well. In this paper, the recent progress in molecular alkaline-earth metal hydrides is reviewed. Reference | Related Articles | Metrics Direct Synthesis of Sulfonated or Sulfenylated Pyrazolones Mediated by KIO3 and Their Anti-microbial Activity Dong Daoqing, Chen Wenjing, Chen Demao, Li Lixia, Li Guanghui, Wang Zuli, Deng Qi, Long Shu Chinese Journal of Organic Chemistry 2019, 39 (11): 3190-3198. DOI: 10.6023/cjoc201904070 Published: 03 July 2019 Abstract (773) HTML (5) PDF (549KB)(828) Knowledge map Fig. & Tab. | Reference | Supporting Info. | Related Articles | Metrics Notes Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization Wang Tieshi, Chen Jianjun, Ye Lin, Zhang Aiying, Feng Zengguo Chin. J. Org. Chem. 2018, 38 (8): 2151-2160. DOI: 10.6023/cjoc201803035 Published: 03 May 2018 Abstract (748) PDF (1372KB)(723) Knowledge map Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh2[R=2-pyridyl (3a), 2-thienyl (3b) and 2-furyl (3c)] and Ph2P-R'-PPh2[R'=2,6-pyridyl (6a), 2,5-thienyl (6b) and 2,5-furyl (6c)] were synthesized. After Staudinger reaction with Me3SiN3, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh2(NSiMe3) and (Me3SiN)Ph2P-R"-PPh2(NSiMe3). The subsequently dehalosilylation reaction with CpTiCl3 afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of 1H NMR, 13C NMR and 31P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane (MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6b produced ultrahigh Mw polyethylene at lower polymerization temperature. Reference | Supporting Info. | Related Articles | Metrics Reviews Experimental and Computational Research Progress on Cycloadditions of o-Carborane with Unsaturated Compounds Mu Weihua, Cheng Ruijiao, Shang Yingwei, He Renze, Li Dongli, Fu Mian Chin. J. Org. Chem. 2018, 38 (6): 1327-1340. DOI: 10.6023/cjoc201712044 Published: 28 February 2018 Abstract (728) PDF (733KB)(978) Knowledge map o-Carboranes, as well as its derivative o-carborynes, can react with a variety of unsaturated compounds through cycloadditions and transform into various functionalized carboranes which have potential applications in many an area such as boron neutron capture therapy, catalytic systhesis and drug design. Recently, people have made remarkable achievements in the functionalization of o-carboranes and o-carborynes, especially in aspects of reaction condition optimization, selectivity controlling and reaction mechanism exploration. The most recent experimental achievements in the area of cycloaddition between o-carboranes and unsaturated compounds, alkenes, polycyclic or heterocyclic aromatics, in the past ten years are summarized. The reaction mechanisms and corresponding computational findings of o-carboryne-involved [2+2+2],[2+2+1],[2+2],[3+2],[4+2] and[5+2] cycloadditions are summarized and emphasized. Moreover, the prospects of future development in this area are discussed in the end. Reference | Related Articles | Metrics Articles Metal-Free Oxidation of Thiols by N-Fluorobenzenesulfonimide: A Rapid and Efficient Method to Synthesize Disulfides Jing Lia, Jin Huia, Guan Meib, Wu Xiaohuaa, Wang Qiantaoa, Wu Yonga Chin. J. Org. Chem. 2018, 38 (3): 692-697. DOI: 10.6023/cjoc201709039 Published: 15 November 2017 Abstract (726) PDF (437KB)(826) Knowledge map A simple and rapid method is developed for the oxidation of thiols to the corresponding disulfides using N-fluorobenzenesulfonimide (NFSI) as the oxidant without any contamination by over oxidation. The synthetic protocol for disulfide bond formation proceeded efficiently under external base-and metal-free conditions with the advantages of simple operation, mild reaction conditions as well as short reaction times. Reference | Supporting Info. | Related Articles | Metrics Notes Synthesis of Vicinal Trifluoromethanesulfonate Substituted Diaryliodonium Salts and Their Anti-bacterial Properties Cui Liyuan, Chen Huangguan, Ma Jingyi, Han Jianwei, Wang Limin Chin. J. Org. Chem. 2019, 39 (1): 270-276. DOI: 10.6023/cjoc201808043 Published: 17 December 2018 Abstract (714) PDF (1796KB)(1094) Knowledge map Diaryliodonium salts with fluorines have potential bioactivity. Vicinal trifluoromethanesulfonate substituted diaryliodonium salts were synthesized for the purpose of studying their anti-bacterial properties aganist Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Bacillus subtilis (B. subtilis). Firstly, their chemical structures were characterized by 1H NMR, 13C NMR, 19F NMR and mass spectra. The minimum inhibitory concentration (MIC) of these compounds was tested by the micro-broth dilution method. The most active 2-((3-fluorophenyl)(((trifluoromethyl)sulfonyl)oxy)-l3-iodanyl)- phenyl trifluoromethanesulfonate (1) containing fluorine group gave the promising results for Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Bacillus subtilis (B. subtilis) (MIC values of 16, 4 and 4 μg·mL-1), which is significantly lower than the commercial antibacterial agent of isothiazolinones. Scanning electron microscope (SEM) analysis sugggested that the compound led to the death of bacteria. Cytotoxicity tests showed that the compound 1 as well as isothiazolinones had a slight effect on the growth of Hela cells in vitro conditions. Reference | Related Articles | Metrics Articles Trifluoromethylthiolation/Oxidation of Styrenes for Facile Synthesis of α-Trifluoromethylthio Acetophenons Wang Jian-Yong, Ma Lan, Li Yan, Wang Xi-Sheng Chin. J. Org. Chem. 2019, 39 (1): 232-237. DOI: 10.6023/cjoc201807052 Published: 12 November 2018 Abstract (711) PDF (513KB)(899) Knowledge map Trifluoromethylthiolation/oxidation of styrenes with easiy-handling AgSCF3 used as the trifluoromethylthiolating reagent has been described, which furnished a series of α-trifluoromethylthio acetophenons. A variety of substituted styrene could be bifunctionalized via radical process in a mixed solvent of dimethyl sulfoxide (DMSO) and CHCl3, with potassium persulfate used as the oxidant under mild conditions. A simple and efficent method for the facile construction of various α-trifluoromethylthio acetophenons is thus demonstrated. Reference | Supporting Info. | Related Articles | Metrics Studies on the Stereoselective Synthesis of Functionalized Allylsilane Compounds Jiang Quan, He Ling, Li Weidong Chinese Journal of Organic Chemistry 2019, 39 (12): 3454-3459. DOI: 10.6023/cjoc201904081 Published: 30 August 2019 Abstract (706) PDF (492KB)(904) Knowledge map Allylsilanes have emerged as synthetically useful intermediates that can undergo a variety of chemical transformations and have been found versatile applications in C-C bond construction as well as in preparation of complex molecules. Exploration on the stereoselective route to functionalized allylsilanes is of great significance for the development of organic synthetic methodology. An efficient pathway to a series of novel alkoxy-substituted homoiodio-allylsilanes via the Julia olefination of silylmethyl cyclopropyl carbinols was described. Carbinols derived from cyclopropyl aryl ketone were evidenced to be superiorer in controlling the stereoselectivity of the products than the alkyl equivalents. Reference | Supporting Info. | Related Articles | Metrics Notes Tetrabutylammonium Iodide Promoted Thioetherification of Arylsulfonylhydrazides with 4-Hydroxycoumarins Zhu Fuyuan, Wang Yanmei, He Mingchuang, Yan Zhaohua, Lin Sen Chin. J. Org. Chem. 2019, 39 (4): 1175-1180. DOI: 10.6023/cjoc201810005 Published: 30 November 2018 Abstract (706) PDF (844KB)(1037) Knowledge map A facile approach for thioetherification of 4-hydroxycoumarins with arylsulfonyl hydrazides promoted by tetrabutylammonium iodide in the presence of hydrochloric acid was developed generating a series of 3-arylthio-4-hydroxycoumarins in 65%~94% yields. Broad scope and easy availability of substrates, simple operation and high yields of products are the advantages of this method. Reference | Supporting Info. | Related Articles | Metrics Articles Phosphine-Catalyzed Formal[6+2] Cycloadditions of α'-Methylene 2-Cyclopentenones Shi Chonghui, Xiao Benxian, Du Wei, Chen Yingchun Chin. J. Org. Chem. 2019, 39 (8): 2218-2225. DOI: 10.6023/cjoc201903061 Published: 21 May 2019 Abstract (706) PDF (576KB)(617) Knowledge map The formal[6+2] cycloaddition reaction of α'-methylene-2-cyclopentenones and 2-alkylidene-1,3-indanediones was developed under the catalysis of tricyclohexyl phosphine, proceeding in a remote γ-regioselective Rauhut-Currier-type reaction followed by a β'-regioselective intramolecular Michael addition process. An array of fused bicyclic frameworks incorperating a spiro-1,3-indanedione motif were produced in fair to good yields of 48%~76% with excellent diastereoseletivity (generally>19:1 dr). This protocol expands the reaction mode of traditional Rauhut-Currier reaction, which might find further application in organic synthesis. Reference | Supporting Info. | Related Articles | Metrics Articles Copper-Catalyzed Hydroxytrifluoromethylthiolation of Arylpropynones Hu Juanjuan, Huang Yangen, Xu Xiuhua, Qing Fengling Chin. J. Org. Chem. 2019, 39 (1): 177-182. DOI: 10.6023/cjoc201808041 Published: 12 November 2018 Abstract (705) PDF (452KB)(844) Knowledge map Recently, the preparation of fluorinated compounds through difunctionalization strategies has become a hot research area in fluorine chemistry. In this work, a copper-catalyzed hydroxytrifluoromethylthiolation of arylpropynones for the synthesis of the corresponding trifluoromethylthiolated enols was developed. The copper salt and solvent are crucial to the yields of this reaction. Under optimized reaction conditions, a series of trifluoromethylthiolated enols were obtained in moderate to good yields. Reference | Supporting Info. | Related Articles | Metrics Reviews Progress in the Synthesis and Applications of Phosphaalkenes Huang Haiyang, Ding Haixin, Xu Shuangshuang, Bai Jiang, Xiao Qiang Chin. J. Org. Chem. 2019, 39 (5): 1263-1276. DOI: 10.6023/cjoc201811038 Published: 31 January 2019 Abstract (704) PDF (810KB)(983) Knowledge map The phosphaalkenes, as an important part of organophosphorus chemistry, play a very important role in the field of homogeneous catalysis and functional materials due to special properties of P=C unit. However, the difficult access to phosphaalkene compounds and their less stability have severely retarded the progress of the phosphaalkene chemistry. In this paper, the recent advances in phosphaalkenes, introducing the properties, synthetic methods, and applications of phosphaalkenes to provide some reference for related researcher are reviewed. Reference | Related Articles | Metrics Cited: CSCD(1) Notes Palladium-Catalyzed Dehydrative Cross Couplings of Stabilized Phosphorus Ylides with Allylic Alcohols Ma Xiantao, Yu Jing, Ma Ruitian, Yan Ran, Zhang Zhenlei Chin. J. Org. Chem. 2019, 39 (3): 830-835. DOI: 10.6023/cjoc201812051 Published: 22 February 2019 Abstract (697) PDF (503KB)(862) Knowledge map A dehydrative cross coupling of ketone-stabilized phosphorus ylides with the readily available allylic alcohols followed by an one-pot Wittig reaction is developed. A range of functional 1,4-dienes could be obtained in 52%~95% isolated yields in the presence of 5 mol% Pd(PPh3) 4 and 20 mol% B(OH) 3. The same method can be extended to ester or nitrile-stabi-lized phosphorus ylides, affording the corresponding 1,4-dienes in moderate yields. Reference | Supporting Info. | Related Articles | Metrics page Page 1 of 2 Total 66 records First page Prev page Next page Last page