- Synthesis of 3-substituted isocoumarin derivatives via CuI-catalyzed reaction of o-bromobenzamides with 1,3-diketones
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An approach to a variety of 3-substituted isocoumarins has been developed. The reaction proceeded from o-bromobenzamide derivatives and 1,3-diketones via CuI-catalyzed reaction in DMF under the action of KOat 120°C without ligands or additives. Georg Thieme Verlag Stuttgart · New York.
- Cai, Shangjun,Wang, Fei,Xi, Chanjuan
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- Synthesis of hexacyclic fused isocoumarin framework through selective domino multicyclizations under catalyst and solvent free conditions
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A novel fused isocoumarin skeleton has been synthesized through selective domino multicyclizations by mixing homothallic acid and 2,3-diphenylacryloyl chloride at 200 °C under catalyst and solvent free reaction conditions. Six fused rings with two stereogenic centers were assembled in a convenient one-pot operation in good yield. The resulting hexacyclic fused isocoumarin skeleton and its stereochemistry was fully characterized and unambiguously confirmed by X-ray diffraction analysis.
- Babar, Tariq Mahmood,Naseer, Muhammad Moazzam,Rauf, Muhammad Khawar,Pervez, Humayun,Ebihara, Masahiro,Rama, Nasim Hasan
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- Cu(OAc)2 catalyzed ultrasound assisted rapid synthesis of isocoumarin derivatives bearing 3-oxobutyl moiety at C-4 position
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A rapid synthesis of isocoumarins has been achieved via the Cu-catalysed cascade reaction involving tandem intramolecular cyclization followed by olefin addition under ultrasound irradiation. The methodology involved one-pot reaction of 2-alkynylbenzoate
- Dandela, Rambabu,Moturu, Krishna Murthy VR.,Pal, Manojit,Pothireddy, Mohanreddy,Ramarao, Sidda,Siddaiah, Vidavalur,Venkateshwarlu, Rapolu
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- Modular synthesis of 3-substituted isocoumarinsviasilver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes
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A method involving silver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes to yield 3-substituted isocoumarins is described. The developed protocol allows convenient access to a range of synthetically useful 3-substituted isocoumarins and related fused heterocyclolactones in good to high yields, using silver tetrafluoroborate as the catalyst, and atmospheric oxygen as the terminal oxidant and the source of endocyclic oxygen. Mechanistic studies suggest the involvement of a free-radical pathway.
- Wu, Hao,Wang, Yi-Chun,Shatskiy, Andrey,Li, Qiu-Yan,Liu, Jian-Quan,K?rk?s, Markus D.,Wang, Xiang-Shan
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p. 6657 - 6664
(2021/08/16)
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- Synthesis and Catalytic Activity of Atrane-type Hard and Soft Lewis Superacids with a Silyl, Germyl, or Stannyl Cationic Center
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The synthesis and isolation of atrane-type molecules 1E+ (E=Si, Ge, or Sn) having a cationic group 14 elemental center are reported. The cations 1E+ act as hard and soft Lewis superacids, which readily interact with various hard and soft Lewis basic substrates. The rigid atrane framework stabilizes the localized positive charge on the elemental center and assists the formation of the well-defined highly coordinated states of 1E+. The cations were applied to the hydrodefluorination, Friedel-Crafts reaction, alkyne cyclization, and carbonyl reduction as Lewis acid catalysts. Most notably, [1Si][ClO4] exhibits unique chemoselectivity that depends on a solvent in the competitive reaction of silyl enol ether with a mixture of benzaldehyde dimethyl acetal and benzaldehyde. Our findings indicate the potential of hard and soft Lewis superacids in organic synthesis.
- Tanaka, Daiki,Konishi, Akihito,Yasuda, Makoto
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supporting information
p. 3118 - 3123
(2021/09/08)
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- Synthesis of 4-Selanyl- And 4-Tellanyl-1 H-isochromen-1-ones Promoted by Diorganyl Dichalcogenides and Oxone
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A new method was developed for the synthesis of 4-chalcogenyl-1H-isochromen-1-ones through the 6-endo-dig electrophilic cyclization of 2-alkynylaryl esters and diorganyl dichalcogenides under ultrasound irradiation. The reactions were performed under mild
- Goulart, Helen A.,Neto, José S. S.,Barcellos, Angelita M.,Silva, Krigor B.,De Moraes, Maiara C.,Jacob, Raquel G.,Lenard?o, Eder J.,Barcellos, Thiago,Perin, Gelson
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p. 14016 - 14027
(2021/05/05)
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- Visible Light-Promoted Magnesium, Iron, and Nickel Catalysis Enabling C(sp3)-H Lactonization of 2-Alkylbenzoic Acids
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A mild and practical C(sp3)-H lactonization protocol has been achieved by merging photocatalysis and magnesium (iron, nickel) catalysis. A diverse range of 2-alkylbenzoic acids with a variety of substitution patterns could be transformed into the corresponding phthalide products. Based on the mechanistic experimentation and reported prior studies, a possible mechanism for the benzylic oxidative lactonization reaction was proposed with the hypothetic photoactive ternary complex formed between the 2-alkylbenzoic acid substrate, magnesium ion, and bromate anion.
- Li, Sasa,Su, Mincong,Sun, Jie,Hu, Kunjun,Jin, Jian
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supporting information
p. 5842 - 5847
(2021/07/31)
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- Transition-metal-free oxidative cyclization reaction of enynals to access pyrane-2-one derivatives
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A novel and efficient metal-free C-H functionalization of enynals is developed to synthesize α-pyrone derivatives via the formation of two C-O bonds. In this project, K2S2O8 has been introduced as an efficient oxygen source and C-H functionalization agent in regioselective oxidative cyclization reaction with a relatively broad substrate scope.
- Abbasi Kejani, Alireza,Ansari, Farzaneh,Armaghan, Mahsa,Balalaie, Saeed,Frank, Walter,Jafarpour, Farnaz,Khosravi, Hormoz
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p. 4263 - 4267
(2021/05/31)
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- Method for synthesizing isocoumarin derivative under catalysis of silver and application of isocoumarin derivative
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The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a method for synthesizing an isocoumarin derivative under catalysis of silver and application of the isocoumarin derivative. According to the method, 2-(phenylethynyl)benzaldehyde is taken as a model substrate, monovalent silver salt is taken as a catalyst, reaction is carried out at the temperature not lower than 30 DEG C, and the isocoumarin derivative is generated. In the field, 2-(phenylethynyl)benzaldehyde is used as a model substrate for the first time, and the isocoumarin derivative is prepared in one step under the catalytic action of the monovalent silver salt. The method is simple, convenient and efficient, the used raw materials are simple, easy to obtain and non-toxic, the steps are few, the conditions are mild, the cost is low, and the method is suitable for large-scale industrial production.
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Paragraph 0058-0069
(2021/05/12)
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- Rhodium catalyzed carbon-hydrogen bond activation reaction for synthesizing isocoumarin derivative
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The invention belongs to the technical field of fine chemicals, and particularly relates to a preparation method of an isocoumarin derivative, and the isocoumarin derivative is a compound shown as a formula (I).
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Paragraph 0074-0077
(2021/04/10)
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- Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature
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Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.
- Kandasamy, Jeyakumar,Lee, Yong Rok,Singh, Adesh Kumar,Venkatesh, Rapelly
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supporting information
p. 7832 - 7837
(2021/09/28)
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- Triflic acid mediated sequential cyclization of ortho-alkynylarylesters with ammonium acetate
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A triflic acid (TfOH) mediated sequential cyclization of ortho-alkynylarylesters and ammonium acetate (NH4OAc) was reported. The reaction took place via a Br?nsted acid-mediated intramolecular cyclization of ortho-alkynylarylesters followed by an ammonium acetate participated substitution reaction, forming isoquinolin-1-ones as the major products. Different from most of the known synthetic methods of isoquinolin-1-ones, no metal catalyst was required in the reported reaction. The regioisomers – isoindolin-1-ones were obtained together with isoquinolin-1-ones in a few cases. The intermediate compounds – isochromen-1-ones and isobenzofuran-1-ones were also isolated. The interconversion experiments showed that the regioisomers formed during the Br?nsted acid induced intramolecular cyclization of ortho-alkynylarylesters. A natural product – ruprechstyril was prepared in a moderate yield employing the new method.
- Domaradzki, Maciej E.,Liu, Xiaochen,Ong, Jiye,Yu, Gyeongah,Zhang, Gan,Simantov, Ariel,Perl, Eliyahu,Chen, Yu
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- Fe(III)-Catalyzed, Cyclizative Coupling between 2-Alkynylbenzoates and Carbinols: Rapid Generation of Polycyclic Isocoumarins and Phthalides and Mechanistic Study
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FeCl3 catalyzed, highly regioselective cyclizative coupling of internal alkynes with alcohols has been reported for the rapid synthesis of structurally divergent, complex isocoumarins and phthalides respectively in intermolecular and intramolecular fashion. This strategy exhibited very high substrate scope and efficiency and proceeds through the simultaneous formation of C?O and C?C bonds. Observations from a series of control experiments supported a) the mechanism as Lewis acid catalyzed dual activation of ester and alcohol, b) the role of carbocation for the enhanced rates of cyclization, i. e., activation of alkyne by carbocation, and c) no role of HCl in the reported cascade process. (Figure presented.).
- Gandhi, Soniya,Baire, Beeraiah
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p. 2651 - 2657
(2020/05/25)
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- Ruthenium(II)-Catalyzed Construction of Isocoumarins via Dual C-H/C-C Activation of Sulfoxonium Ylides
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A ruthenium(II)-catalyzed annulation between two molecules of sulfoxonium ylides is achieved, generating a variety of substituted isocoumarins in reasonable yields. This strategy features dual C-H/C-C activation in one pot and has a wide substrate scope and good functional group tolerance.
- Wen, Si,Chen, Yanhui,Zhao, Zemin,Ba, Dan,Lv, Weiwei,Cheng, Guolin
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p. 1216 - 1223
(2020/01/09)
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- Palladium complexes with an annellated mesoionic carbene (MIC) ligand: Catalytic sequential Sonogashira coupling/cyclization reaction for one-pot synthesis of benzofuran, indole, isocoumarin and isoquinolone derivatives
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Two Pd(ii) complexes (1 and 2) featuring a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand have been synthesized and structurally characterized. Both complexes effectively catalyze the one-pot synthesis of benzofuran starting from phenylacetylene and 2-iodophenol under mild conditions. Complex 1 is found to be an excellent catalyst for the straightforward access to a library of benzofuran, indole, isocoumarin and isoquinolone derivatives by the reaction of terminal alkynes with 2-iodo derivates of phenol, N-methyl aniline, benzoic acid and N-methyl benzamide, respectively. The general utility of the catalytic method is demonstrated using a variety of diversely substituted terminal alkynes and the corresponding desired products are obtained in good to excellent yields. On the basis of control experiments, a two-cycle mechanism is proposed which involves the Sonogashira coupling of 2-iodo derivatives with alkynes and the subsequent cyclization of the corresponding 2-alkynyl compounds.
- Bera, Jitendra K.,Daw, Prosenjit,Reshi, Noor U Din,Tyagi, Akshi
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supporting information
p. 15238 - 15248
(2020/11/18)
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- Regioselective Chlorolactonization of Styrene-Type Carboxylic Esters and Amides via PhICl2-Mediated Oxidative C-O/C-Cl Bond Formations
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A facile method employing styrene-type carboxylic esters or amides in the presence of PhICl2 in CH3CN was developed to achieve the synthesis of 6-endo products 3,4-dihydroisocoumarins or 3,4-dihydroisocoumarin-1-imines in good to hig
- Xing, Linlin,Zhang, Yong,Zhang, Yilin,Ai, Zhenkang,Li, Xuemin,Du, Yunfei,Deng, Jun,Zhao, Kang
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p. 13832 - 13840
(2019/10/17)
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- An Unusual Conversion of 2-(Alkynonyl)Alkynylbenzenes to Isocoumarins by a Retro-Favorskii-like Degradation
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We report the discovery of an anomalous reaction of 2-(alkynonyl)alkynylbenzenes under AgI catalysis for the selective formation of isocoumarins. This reaction is previously undocumented for 2-(alkynonyl)alkynylbenzenes in terms of the reaction mechanism and the product formed. Water (H2O18) labeling studies suggested a possible mechanistic pathway in which the initial formation of a pyrylium ion is followed by hydrative dealkynylation, that is, water incorporation and alkyne expulsion, similar to a retro-Favorskii reaction.
- Santhi, Jampani,Baire, Beeraiah
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supporting information
p. 3161 - 3165
(2019/09/17)
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- Gold-Catalyzed Oxidation of Internal Alkynes into Benzils and its Application for One-Pot Synthesis of Five-, Six-, and Seven-Membered Azaheterocycles
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Internal alkynes have been shown to undergo oxidation to substituted benzils (1,2-diarylethane-1,2-diones) by α-picoline N-oxide in the presence of Ph3PAuNТf2 (5 mol-%). In addition to the unsubstituted benzil, the method allows preparing, under markedly mild conditions (50 °C in chlorobenzene), various non-symmetrical products, including heteroaromatic versions thereof which are much more difficult to obtain otherwise. This gold(I)-catalyzed transformation was integrated into one-pot reaction sequence delivering a range of 5- to 7-membered ring systems (imidazoles, quinoxalines, 1,2,4-triazines, pyrazines, and 1,4-diazepines), thus linking these important heterocyclic motifs to the internal alkyne reagent space.
- Dubovtsev, Alexey Yu.,Dar'in, Dmitry V.,Krasavin, Mikhail,Kukushkin, Vadim Yu.
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p. 1856 - 1864
(2019/02/19)
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- Lactonization of 2-Alkynylbenzoates for the Assembly of Isochromenones Mediated by BF3·Et2O
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A general and efficient lactonization method of readily available 2-alkynylbenzoates affording biologically important isochromenones has been realized via a solely BF3·Et2O-mediated 6-endo-dig cyclization process under mild condition
- Zhang, Xiang,Wan, Xintong,Cong, Ying,Zhen, Xiaohua,Li, Qiao,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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p. 10402 - 10411
(2019/08/20)
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- Synthesis of 4-chloroisocoumarins via intramolecular halolactonization of o-alkynylbenzoates: PhICl2-mediated C-O/C-Cl bond formation
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A series of 4-chloroisocoumarins were conveniently synthesized from o-alkynylbenzoates via PhICl2-mediated intramolecular cyclization under metal-free conditions. PhICl2 plays the role of both the oxidant and the chlorine source to e
- Xing, Linlin,Zhang, Yong,Li, Bing,Du, Yunfei
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p. 1989 - 1993
(2019/03/26)
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- Ruthenium(II)-Catalyzed Homocoupling of Weakly Coordinating Sulfoxonium Ylides via C?H Activation/Annulations: Synthesis of Functionalized Isocoumarins
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Homocoupling of weakly coordinating sulfoxonium ylides was accomplished via ruthenium (II) catalyzed C?H activation process. This strategy provides a convenient, efficient and step-economic method to access 3-substituted isocoumarins with good functional
- Zhou, Ming-Dong,Peng, Zhen,Wang, He,Wang, Zhao-Hui,Hao, Da-Jin,Li, Lei
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p. 5191 - 5197
(2019/11/13)
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- Sulfoxonium Ylides as Carbene Precursors: Rhodium(III)-Catalyzed Sequential C?H Functionalization, Selective Enol Oxygen-Atom Nucleophilic Addition, and Hydrolysis
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Herein, we report a protocol for Rh(III)-catalyzed annulation reactions between oxazolines and sulfoxonium ylides via a sequence involving C?H activation, selective enol oxygen-atom nucleophilic addition, and hydrolysis. This practical, operationally simple protocol has a wide substrate range, excellent regioselectivity, and moderate to good yields.
- Huang, Yuanqiong,Lyu, Xueli,Song, Hongjian,Wang, Qingmin
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supporting information
p. 5272 - 5276
(2019/11/13)
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- Oxidative: Oxy -cyclization of 2-alkynylbenzamide enabled by TBAB/Oxone: Switchable synthesis of isocoumarin-1-imines and isobenzofuran-1-imine
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A TBAB-catalyzed oxidative 6-endo-dig oxy-cyclization of 2-alkynylbenzamide is described herein for the synthesis of isocoumarin-1-imines. The transformation proceeds regioselectively and provides the final products with high efficiency and a broad reacti
- Wang, Yan-Hua,Ouyang, Banlai,Qiu, Guanyinsheng,Zhou, Hongwei,Liu, Jin-Biao
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supporting information
p. 4335 - 4341
(2019/05/06)
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- Ruthenium catalytic 3-substituted isocoumarin synthesis method
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The invention discloses a ruthenium catalytic 3-substituted isocoumarin synthesis method, wherein ruthenium is used as a catalyst, the ortho C-H bond activation of an aromatic hydrocarbon and an intramolecular ring closing reaction are achieved under weak
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Paragraph 0052-0056; 0077-0084
(2019/11/04)
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- Fluorination-triggered tandem cyclization of styrene-type carboxylic acids to access 3-aryl isocoumarin derivatives under microwave irradiation
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A practical and straightforward synthetic route through a fluorination-triggered tandem cyclization of styrene-type carboxylic acids was developed to construct a variety of 4-fluoro-3-aryl-3,4-dihydroisocoumarins and 3-arylisocoumarins under microwave irr
- Yuan, Jinwei,Zeng, Fanlin,Mai, Wenpeng,Yang, Liangru,Xiao, Yongmei,Mao, Pu,Wei, Donghui
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p. 5038 - 5046
(2019/06/03)
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- 1-Phenyl-1,2-benziodoxol-3-(1H)-one as Synthon for Phthalide Synthesis through Pd-Free, Base-Free, Sonogashira-Type Coupling Cyclization Reaction
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Hypervalent iodine(III) five-membered heterocycles have found broad application as atom-transfer reagents for organic synthesis. Among them, 1-phenyl-1,2-benziodoxol-3-(1H)-one is known as a traditional benzyne precursor, but no further synthetic applicat
- Almasalma, Ahmad A.,Mejía, Esteban
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p. 188 - 195
(2017/11/30)
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- Silver triflate/: P -TSA co-catalysed synthesis of 3-substituted isocoumarins from 2-alkynylbenzoates
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In this paper, we describe the silver triflate/p-toluenesulfonic acid co-catalysed synthesis of seventeen isocoumarins and two thieno[2,3-c]pyran-7-ones starting from 2-alkynylbenzoates and 3-alkynylthiophene-2-carboxylates, respectively. The reaction proceeds with absolute regioselectivity under mild reaction conditions and low catalyst loading, to afford the desired products in good to excellent yields. A conceivable reaction mechanism is proposed and supported by isotope-exchange tests, 1H NMR studies and ad hoc experiments.
- Gianni, Jonathan,Pirovano, Valentina,Abbiati, Giorgio
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supporting information
p. 3213 - 3219
(2018/05/17)
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- Cp?Co(III)-Catalyzed C-H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors
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A Cp?Co(III)-catalyzed C-H bond functionalization of a range of arenes by employing sulfoxonium ylides as carbene precursors instead of diazo compounds and other carbene precursors has been established. This reaction is highly efficient without any additi
- Ji, Shuying,Li, Bin,Wang, Baiquan,Yan, Kelu
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supporting information
p. 5981 - 5984
(2018/09/29)
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- Ruthenium(IV) Intermediates in C?H Activation/Annulation by Weak O-Coordination
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Ruthenium(IV) complexes were identified as key intermediates of C?H/O?H activations by weak O-coordination. Thus, the annulations of sulfoxonium ylides by benzoic acids provided expedient access to diversely-decorated isocoumarins with ample scope. Detailed experimental and computational studies provided strong support for a facile BIES-C?H activation, along with cyclometalated ruthenium(IV) intermediates within a versatile ruthenium(II/IV) catalysis regime (BIES=base-assisted internal electrophilic substitution).
- Liang, Yu-Feng,Yang, Long,Rogge, Torben,Ackermann, Lutz
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supporting information
p. 16548 - 16552
(2018/10/26)
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- Medical intermediate diaryl ethylene oxide compound and synthesis method thereof
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The invention relates to a medical intermediate namely a diaryl ethylene oxide compound shown by the formula (I) as shown in the specification and a synthesis method thereof, wherein R1 is selected from H, halogen or C1-C6 alkyl; and R2 is selected from H, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkyl or halogenated C1-C6 alkoxy. The invention also relates to a synthesis method of the derivative. The diaryl ethylene oxide compound can be used for one-step synthesis of isocoumarin compounds, thus having good application prospect and research value in the field of synthesis of theisocoumarin compounds.
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- Synthetic method of isocoumarin medicament intermediate
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The invention relates to a synthetic method of an isocoumarin medicament intermediate as shown in the following formula (I). The method comprises the following steps: under existence of a palladium compound catalyst and an acidic compound, in a solvent, a reaction is carried out for a compound as shown in the following formula (II), after the reaction ends, an isocoumarin medicament intermediate as shown in the formula (I) is obtained, wherein R1 is selected from H, halogen, or C1-C6 alkyls; R2 is selected from H, halogen, C1-C6 alkyls, C1-C6 alkoxys, halogenated C1-C6 alkyls or halogenated C1-C6 alkoxys. The method employs specific catalysts, acidic compounds and solvents, in order to provide good technical effects. The invention also provides a novel synthetic method of the compound in the formula (II) as a reactant, in order to provide a simple preparation method for synthesis of the isocoumarin medicament intermediate, and the method has good application prospects and research values.
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- Preparation method of isocoumarin medicament intermediate
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The invention relates to a preparation method of an isocoumarin medicament intermediate as shown in the following formula (5). The method has a reaction route as follows, and the method comprises thefollowing steps: S1: a compound in a formula (1) and a compound in a formula (2) are reacted under the existence of a palladium catalyst, a cationic ammonium compound, and alkali in an organic solvent, after the reaction ends, aftertreatment is carried out, in order to obtain a compound in a formula (3); S2: in an organic solvent, under the existence of an oxidizing agent, a self cyclization reaction of the compound in the formula (3) is carried out, and after the reaction ends, aftertreatment is carried out in order to obtain a compound in a formula (4); S3: under the existence of the palladium compound catalyst and the acidic compound, in a solvent, a reaction is carried out for the compound in the formula (4), and after the reaction ends, aftertreatment is carried out in order to obtainthe isocoumarin medicament intermediate as shown in the formula (5). According to the method, multiple technical characteristics of each step can be subjected to creative optimization, a whole new synthetic method and synthetic route is provided for preparing the isocoumarin compound, and the method has good industrialization prospect and latent application values.
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- Divergent Syntheses of (Z)-3-Alkylideneisobenzofuran-1(3 H)-ones and 1 H-Isochromen-1-ones by Copper-Catalyzed Cycloisomerization of 2-Alkynylbenzoic Acids in Ionic Liquids
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The cycloisomerization of readily available 2-alkynylbenzoic acids 1 in ionic liquids (ILs) as recyclable reaction media has been studied under the catalytic action of CuCl2. With substrates bearing an aryl group on the triple bond, a mixture o
- Mancuso, Raffaella,Pomelli, Christian S.,Chiappetta, Piera,Gioia, Katia F.,Maner, Asif,Marino, Nadia,Veltri, Lucia,Chiappe, Cinzia,Gabriele, Bartolo
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p. 6673 - 6680
(2018/06/01)
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- Rhodium(III)-catalyzed chemodivergent annulations between: N-methoxybenzamides and sulfoxonium ylides via C-H activation
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Chemodivergent and redox-neutral annulations between N-methoxybenzamides and sulfoxonium ylides have been realized via Rh(iii)-catalyzed C-H activation. The sulfoxonium ylide acts as a carbene precursor, and coupling occurs under acid-controlled condition
- Xu, Youwei,Zheng, Guangfan,Yang, Xifa,Li, Xingwei
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supporting information
p. 670 - 673
(2018/01/28)
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- Cp?Co(III)-Catalyzed C-H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors
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A Cp?Co(III)-catalyzed C-H bond functionalization of a range of arenes by employing sulfoxonium ylides as carbene precursors instead of diazo compounds and other carbene precursors has been established. This reaction is highly efficient without any additi
- Ji, Shuying,Yan, Kelu,Li, Bin,Wang, Baiquan
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supporting information
(2018/09/27)
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- Reaction of arynes with trifluoroacetylated β-diketones: Novel formation of isocoumarins and phenanthrenes
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Polysubstituted isocoumarins were synthesized by the reaction of substituted 2-(trimethylsilyl)aryl triflates with trifluoromethylated β-diketones in the presence of CsF. The reaction proceeded through carbon-carbon bond insertion of aryne and intramolecular cyclization to form intermediates of alcohol anions, which extruded trifluoromethyl anion to afford isocoumarins. By using CuBr as a catalyst, 2 eq. of aryne reacted with β-diketones to afford phenanthrenes and 1,2-diarylethanones. Although reaction of 2-(trimethylsilyl)phenyl triflate with 1,1,1-trifluoro-4′-methylbenzoylacetone in the presence of CsF gave 3-(4′-methylphenyl)isocoumarin in 67% yield, addition of 0.2 eq. of CuCN resulted in the formation of 9-(4-methylbenzoyl)-10-trifluoromethylphenanthrene in 35% yield.
- Okuma, Kentaro,Tanabe, Yukiko,Fukami, Takuto,Ishibashi, Yuto
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- A highly active diradical cobalt(iii) catalyst for the cycloisomerization of alkynoic acids
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The first cobalt-catalysed cycloisomerisation of alkynoic acids is reported, thanks to the design of a well-defined diradical cobalt(iii) catalyst, in the absence of any additives. The high efficiency, regioselectivity and chemoselectivity are comparable to those of noble metal-based systems. The unique reactivity might be attributed to second coordination sphere effects.
- Leconte, Nicolas,Du Moulinet D'Hardemare, Amaury,Philouze, Christian,Thomas, Fabrice
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supporting information
p. 8241 - 8244
(2018/07/29)
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- PtO2/PTSA system catalyzed regioselective hydration of internal arylalkynes bearing electron withdrawing groups
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A highly efficient PtO2/PTSA catalyst system for the hydration of a wide array of alkynes was developed. This method proved to be compatible with a large range of functional groups and the ketone products were obtained in high yields. The scope of this methodology was also extended to the synthesis of 3-Aryl-isochromenones,-indoles and-benzofurans.
- Lin, Hsin-Ping,Ibrahim, Nada,Provot, Olivier,Alami, Mouad,Hamze, Abdallah
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p. 11536 - 11542
(2018/04/05)
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- Palladium-catalyzed carbonylative synthesis of isocoumarins and phthalides by using phenyl formate as a carbon monoxide source
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A simple and efficient palladium-catalyzed intramolecular carbonylative synthesis of isocoumarins and phthalides from the easily available starting materials by employing phenyl formate as a CO surrogate has been achieved. The approach affords target compounds in good to excellent yields with the advantages of lower toxicity, milder conditions, easy operation and wide functional group tolerance.
- Yuan, Qing,Chen, Zhen-Bang,Zhang, Fang-Ling,Zhu, Yong-Ming
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p. 1628 - 1635
(2017/02/23)
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- Copper-Catalyzed Acyloxycyanation of Alkynes with Acetonitrile: Regioselective Construction of Cyclic Acrylonitriles by 6-endo or 5-exo Cyclization
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An efficient difunctionalization of alkynes by tandem iodolactonization and copper-catalyzed cyanation using acetonitrile as a cyanating reagent is reported for the first time. This approach can afford cyano-containing isocoumarin or phthalide derivatives
- Zhu, Yamin,Shen, Zengming
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p. 3515 - 3519
(2017/09/13)
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- Hydroiodination-Triggered Cascade Reaction with I2/PPh3/H2O: Metal-Free Access to 3-Substituted Phthalides from 2-Alkynylbenzoates
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Phthalide is an important scaffold found in several biologically active compounds. Therefore, effective methods for the synthesis of phthalides are strongly desired. Herein, we describe the metal-free synthesis of 3-substituted phthalides by the reductive hydroiodination of 2-alkynylbenzoates through an I2/PPh3/H2O-triggered cascade reaction. A variety of 3-substituted phthalides were synthesized in excellent yields by a one-pot reaction involving four processes: desilylation, hydroiodination, cyclization, and reduction.
- Kawaguchi, Shin-Ichi,Nakamura, Kentaro,Yamaguchi, Kotaro,Sato, Yuki,Gonda, Yuhei,Nishioka, Masaaki,Sonoda, Motohiro,Nomoto, Akihiro,Ogawa, Akiya
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supporting information
p. 5343 - 5346
(2017/09/06)
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- On-Water Silver(I)-Catalyzed Cycloisomerization of Acetylenic Free Amines/Amides towards 7-Azaindole/Indole/Isoquinolone Derivatives
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Silver-catalyzed on-water intramolecular cyclization of acetylenic free amines is reported, which affords 7-azaindoles in good to excellent yields. Neither strong base/acid catalysts nor N-substituted substrates are required to achieve this cycloisomerization. Hydrogen bonds between water medium and the substrates play an important role in improving chemical reactivity and regioselectivity. Furthermore, the on-water reaction is extendable to acetylenic amides for isoquinolone synthesis.
- Sun, Hongpeng,Xiao, Li,Li, Wei,Xie, Qiong,Shao, Liming
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supporting information
p. 4845 - 4852
(2017/10/06)
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- Palladium-Catalyzed Sequential Nucleophilic Addition/Oxidative Annulation of Bromoalkynes with Benzoic Acids to Construct Functionalized Isocoumarins
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An efficient and robust protocol for the preparation of 3-substituted isocoumarins via palladium-catalyzed nucleophilic addition/oxidative annulation of bromoalkynes with benzoic acids has been developed. Remarkably, preliminary mechanistic studies indicated that the transformation might proceed via a stereo- and regioselective nucleophilic addition and C-H functionalization procedure.
- Jiang, Guangbin,Li, Jianxiao,Zhu, Chuanle,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 4440 - 4443
(2017/09/11)
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- Copper-catalyzed annulation of 2-bromobenzoic esters with terminal alkynes towards 3-substituted isocoumarins
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An efficient method for the synthesis of 3-substituted isocoumarins that are an important class of biologically active scaffolds via annulation of 2-bromobenzoic esters with terminal alkynes by copper catalyzed is described. The advantages of this method include mild reaction conditions, high yield and regioselectivity, and wide tolerance toward functional groups.
- Sun, Mengli,Su, Lebin,Dong, Jianyu,Liu, Long,Zhou, Yongbo,Yin, Shuang-Feng
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p. 2433 - 2437
(2017/05/31)
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- Ruthenium-NHC-Diamine Catalyzed Enantioselective Hydrogenation of Isocoumarins
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A novel and practical chiral ruthenium-NHC-diamine system is disclosed for the enantioselective hydrogenation of isocoumarins, which provides a new concept to apply (chiral) NHC ligands in asymmetric catalysis. A variety of optically active 3-substituted 3,4-dihydroisocoumarins were obtained in excellent enantioselectivities (up to 99% ee). Moreover, this methodology was utilized in the synthesis of O-methylmellein, mellein, and ochratoxin A.
- Li, Wei,Wiesenfeldt, Mario P.,Glorius, Frank
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supporting information
p. 2585 - 2588
(2017/03/08)
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- A aqueous phase catalytic cascade reaction in the synthesis of isocoumarin derivatives of the method (by machine translation)
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The invention provides a method for the aqueous phase catalytic cascade reaction in the synthesis of isocoumarin derivatives of the method, which is based on the concentration in the aqueous phase is 0.1 — 1 mol/L of ortho-halo benzoic acid 1 μM with 0.1 μM — 5 μM terminal alkyne in of 0.001 μM — 1 μM catalyst bivalent copper salt and O-phenanthrene under the catalytic action of, in 0.5 μM — 6 μM inorganic base or organic base in the presence of, in 20o C — 160 o C lower reaction 1h — 50h one pot synthesis isocoumarin derivatives. The invention is an environment-friendly, the operation is simple, cheap and safe, efficient to prepare the isocoumarin compound of the novel method, compared with the prior art, not only can be applied to a large number of functional groups, but also with simple operation, high yield, single product, convenient separation and purification, safe and cheap, small pollution and the like. (by machine translation)
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Paragraph 0055-0056
(2017/08/23)
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- Enantioselective Synthesis of 1,2-Dihydronaphthalenes via Oxidative N-Heterocyclic Carbene Catalysis
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1,2-Dihydronaphthalenes are important molecules in both medicinal and synthetic chemistry, but methods for the catalytic asymmetric construction of this class of molecules are limited. The diastereo- and enantioselective N-heterocyclic carbene-catalyzed cascade annulation reactions using benzodiketones and enals under oxidative conditions, which afford a variety of 1,2-dihydronaphthalenes with two adjacent stereocenters in up to 99% yield, with >20:1 dr, and up to 99% ee, are reported. Furthermore, the product can be easily transformed to a series of useful compounds such as alcohol, amide, and epoxide.
- Perveen, Saima,Zhao, Zhifei,Zhang, Guoxiang,Liu, Jian,Anwar, Muhammad,Fang, Xinqiang
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supporting information
p. 2470 - 2473
(2017/05/24)
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- Pd-Catalyzed/Iodide-Promoted α-Arylation of Ketones for the Regioselective Synthesis of Isocoumarins
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A variety of isocoumarins have been synthesized directly from 2-halobenzoates and ketones through a palladium-catalyzed α-arylation step followed by an intramolecular cyclization process. The addition of iodide anions to the reaction mixture increased yields and selectivities especially when 2-bromobenzoates were employed. This phosphine-free one-pot synthesis features a high functional group tolerance and gives access to richly decorated isocoumarins. This general methodology was successful in the total synthesis of Xyridin A, an important natural product with antibacterial and antifungal activity.
- Casnati, Alessandra,Maggi, Raimondo,Maestri, Giovanni,Della Ca, Nicola,Motti, Elena
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supporting information
p. 8296 - 8303
(2017/08/14)
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- Copper nanoparticles catalyzed economical synthesis of 3-substituted isocoumarins from 2-chlorobenzoic acids/amides and 1,3-diketones
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Copper nanoparticles were utilized as a highly efficient catalyst for a facile and economical synthesis of 3-substituted isocoumarins with 2-chlorobenzoic acids and 1,3-diketones as starting materials. The copper nanoparticles catalyst showed highly catalytic activity for the 2-chloro-substituted substrates to afford 3-substituted isocoumarins in good to excellent yields. Furthermore, good catalytic activity was also observed when 2-chlorobenzoic amides were utilized as substrates instead of the benzoic acids.
- Wang, Xiaowen,Wu, Chaolong,Sun, Youwen,Yao, Xiaoquan
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supporting information
p. 3164 - 3167
(2017/07/18)
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- Triaryl-Like MONO-, BIS-, and TRISKITPHOS Phosphines: Synthesis, Solution NMR Studies, and a Comparison in Gold-Catalyzed Carbon-Heteroatom Bond Forming 5-exo-dig and 6-endo-dig Cyclizations
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A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence of increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon-heteroatom bond-forming cyclizations has been investigated. Detailed solution NMR studies on Ph-TRISKITPHOS, its oxide, and the corresponding gold(I) chloride adduct identified a conformational exchange process involving a concerted librational motion of the individual anthracene-derived organic substituents about their P-C bonds. The cessation of this motion at reduced temperatures lowers the molecular symmetry such that the two C6H4 rings in each of the KITPHOS units become inequivalent; a lower energy process involving restricted rotation of the biaryl-like phenyl ring has also been identified. Electrophilic gold(I) complexes of these triaryl-like KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of propargyl amides to afford the corresponding methylene oxazolines, which were used in a subsequent tandem carbonyl-ene reaction to afford functionalized 2-substituted oxazolines. A comparative survey revealed that catalyst efficiency for cycloisomerization decreases in the order MONOKITPHOS = BISKITPHOS > PPh3 > TRISKITPHOS. The optimum system also catalyzes the selective 6-endo-dig cyclization of 2-alkynylbenzyl alcohols, 2-alkynylbenzoic acid, and 2-phenylethynyl benzamides; gratifyingly, in several cases the yields obtained are markedly higher and/or reaction times significantly shorter than those previously reported for related gold catalysts. Moreover, these are the first examples of gold(I)-catalyzed 6-endo-dig cycloisomerizations involving 2-phenylethynyl benzamides and, reassuringly, the optimum gold(I)/MONOKITPHOS systems either rivaled or outperformed existing silver or palladium-based catalysts. The steric parameters of this homologous series of phosphines have been quantified and compared with selected triarylphosphines using a combination of Solid-G calculations, to determine the percentage of the metal coordination sphere shielded by the phosphine (the G parameter), and Salerno molecular buried volume calculations (SambVca) to determine the percent buried volume (%Vbur); the corresponding Tolman cone angles have also been determined from correlations.
- Doherty, Simon,Knight, Julian G.,Perry, Daniel O.,Ward, Nicholas A. B.,Bittner, Dror M.,McFarlane, William,Wills, Corinne,Probert, Michael R.
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p. 1265 - 1278
(2016/06/01)
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- Inhibition of the enzymes in the leukotriene and prostaglandin pathways in inflammation by 3-aryl isocoumarins
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The biosynthesis of leukotrienes in one of the arachidonic acid pathways and PGE2in the other by 5-LOX and mPGES1 respectively, play pivotal roles in augmenting inflammatory responses. PGE2is known to participate in cancer pathologic
- Ramanan, Meera,Sinha, Shweta,Sudarshan, Kasireddy,Aidhen, Indrapal Singh,Doble, Mukesh
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p. 428 - 434
(2016/09/09)
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- Manganese-Catalyzed ortho-C?H Alkenylation of Aromatic N?H Imidates with Alkynes: Versatile Access to Mono-Alkenylated Aromatic Nitriles
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So far, the direct C?H alkenylation of aromatic nitriles with alkynes has not been achieved. Herein, we discribe the first manganese-catalyzed C?H alkenylation of aromatic N?H imidates to access mono-alkenylated aromatic nitriles. The reaction is accelerated by the presence of a catalytic amount of sodium pivalate. This protocol is also highlighted by the simple catalytic system, good compatibility of functional groups, and excellent mono-/dialkenylation selectivity as well as E/Z stereoselectivity. (Figure presented.).
- Yang, Xiaoxu,Jin, Xiqing,Wang, Congyang
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p. 2436 - 2442
(2016/08/16)
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