- Rh2(OAc)4-catalyzed regioselective intermolecular C-H insertion reactions: Novel synthesis of 2-pyrrol-3′-yloxindoles
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Regioselective synthesis of 2-pyrrol-3′-yloxindoles has been achieved by the reactions of cyclic diazo carbonyl compounds la-e with pyrrole and substituted pyrroles (2a-d) in the presence of rhodium(II) acetate catalyst via intermolecular C-H insertion reaction.
- Muthusamy, Sengodagounder,Gunanathan, Chidambaram
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- Stereoselective epoxide generation with cyclic rhodium carbenoids: A new access to spiro-indolooxiranes
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The reaction of cyclic diazoamides with aryl aldehydes catalyzed by rhodium(II) acetate leads to intermolecular stereoselective epoxide ring formation. A series of spiro-indolooxiranes has been synthesized following the described method in a facile manner. The use of aryl dialdehydes in the course of reaction of cyclic diazoamide resulted the formation of bis-spiro- indolooxiranes.
- Muthusamy, Sengodagounder,Gunanathan, Chidambaram,Nethaji, Munirathinam
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- Visible-Light-Mediated Cyclopropanation Reactions of 3-Diazooxindoles with Arenes
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The cyclopropanation reaction of 3-diazooxindoles with arenes was first accomplished using visible-light irradiation. A series of spiro[norcaradiene-7,3′-indolin]-2′-ones were synthesized for the first time in high yields and with excellent diastereoselectivities. The synthetic usefulness of this catalyst-free photochemical methodology is illustrated by the further controllable rearrangement and epoxidation reactions.
- Zhao, Shuai,Chen, Xiang-Xiang,Gao, Nan,Qian, Mingcheng,Chen, Xin
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- Highly diastereoselective synthesis of dispiro[1,4-dithiane/dithiepane] bisoxindoles via Stevens rearrangement
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Synthesis of dispiro[1,4-dithianes/dithiepanes]bisoxindoles from the reaction of 3-diazo-2-oxindoles and spiro-1,3-dithiolaneoxindole or -1,3-dithianeoxindole derivatives in the presence of rhodium(II) acetate dimer as a catalyst was demonstrated under mild conditions in a highly diastereoselective manner. These dispiro-compounds were obtained via intermolecular sulfonium ylides and followed by Stevens rearrangement.
- Muthusamy, Sengodagounder,Selvaraj, Karuppu
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- Divergent Synthesis of Aziridine and Imidazolidine Frameworks under Blue LED Irradiation
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We develop a visible light-promoted divergent cycloaddition of α-diazo esters with hexahydro-1,3,5-triazines, leading to a series of aziridine and imidazolidine frameworks in average good yield, by simply changing the reaction media used. It is noteworthy that the reaction occurs under sole visible light irradiation without the need for exogenous photoredox catalysts. More significantly, a reasonable reaction mechanism was proposed on the basis of the control experiments and density functional theory calculation results.
- Cheng, Xiao,Cai, Bao-Gui,Mao, Hui,Lu, Juan,Li, Lei,Wang, Kun,Xuan, Jun
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p. 4109 - 4114
(2021/05/26)
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- Copper-Catalyzed Oxidation of Hydrazones to Diazo Compounds Using Oxygen as the Terminal Oxidant
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A mild method for accessing diazo compounds via aerobic oxidation of hydrazones is described. This catalytic transformation employs a Cu(OAc)2/pyridine catalyst and molecular oxygen from ambient air as the terminal oxidant, generating water as the sole byproduct and affording the desired diazo compounds within minutes at room temperature. A broad array of electronically diverse aryldiazo esters, ketones, and amides can be accessed. Pyridine dramatically enhances the rate of the reaction by solubilizing the copper catalyst and serving as the Br?nsted base in the turnover-limiting proton-coupled oxidation of hydrazone by copper(II). Insights gained from mechanistic studies led to expansion of the scope of this method to include diaryl hydrazones, delivering diaryl diazomethane derivatives, which cannot be accessed via established diazo transfer methods. The products of this method may be employed in rhodium carbene catalysis without isolation of the diazo intermediate to afford cyclopropane products in good yield with high enantioselectivity.
- Liu, Wenbin,Twilton, Jack,Wei, Bo,Lee, Maizie,Hopkins, Melissa N.,Bacsa, John,Stahl, Shannon S.,Davies, Huw M. L.
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p. 2676 - 2683
(2021/03/03)
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- Construction of 2-alkynyl aza-spiro[4,5]indole scaffolds: Via sequential C-H activations for modular click chemistry libraries
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Herein, we have developed a strategy of sequential C-H activations of indole to construct novel 2-alkynyl aza-spiro[4,5]indole scaffolds, which incorporated both alkyne and spiro-units into indole. Gram-scale synthesis and a one-pot, three-step synthesis demonstrated the utility of this protocol. Hybrid conjugates with an oseltamivir derivative further offered a powerful tool for the construction of a versatile spiroindole-containing library via click chemistry. This journal is
- Zhang, Jun,Wang, Mengmeng,Wang, Huiying,Xu, Hui,Chen, Junjie,Guo, Ziqiong,Ma, Biao,Ban, Shu-Rong,Dai, Hui-Xiong
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p. 8656 - 8659
(2021/09/04)
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- Synthesis of (Z)-3-[amino(phenyl)methylidene]-1,3-dihydro-2Hindol-2-ones using an Eschenmoser coupling reaction
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A highly modular method for the synthesis of (Z)-3-[amino(phenyl/methyl)methylidene]-1,3-dihydro-2H-indol-2-ones starting from easily available 3-bromooxindoles or (2-oxoindolin-3-yl)triflate and thioacetamides or thiobenzamides is described. A series of 49 compounds, several of which have previously been shown to possess significant tyrosin kinase inhibiting activity, was prepared in yields varying mostly from 70 to 97% and always surpassing those obtained by other published methods. The method includes an Eschenmoser coupling reaction, which is very feasible (even without using a thiophile except tertiary amides) and scalable. The (Z)configuration of all products was confirmed by NMR techniques.
- Marek, Luká?,Kolman, Luká?,Váňa, Ji?í,Svoboda, Jan,Hanusek, Ji?í
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p. 527 - 539
(2021/03/31)
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- Diastereoselective Palladium Catalyzed Carbenylative Amination of ortho-Vinylanilines with 3-Diazoindolin-2-ones
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A diastereoselective palladium catalyzed carbenylative amination of ortho-vinylaniline with 3-diazoindolines-2-one have been accomplished for the synthesis of various tetrasubstituted indoline fused spirooxindole with good yields and diastereoselectivity. Notable features of the method include construction of two contiguous tetrasubstituted carbon stereocenters via C?N and C?C bond formation in single operation, wide functional group tolerance and high atom and step economy. Importantly, the present reaction was also extended to one-pot conversion of tosylhydrazones and ortho-vinylanilines to spirooxindole derivatives. (Figure presented.).
- Reddy, Angula Chandra Shekar,Reddy, Palagulla Maheswar,Anbarasan, Pazhamalai
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p. 801 - 806
(2020/01/25)
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- Photochemical O?H Functionalization Reactions of Cyclic Diazoamides
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Herein, we describe the photochemical O?H functionalization reaction of acidic alcohols with cyclic diazoamides. We studied the O?H functionalization reaction of different fluorinated and non-fluorinated alcohols to give the corresponding ether products in high yields (43 examples, up to 97% yield). Furthermore, we performed studies to evaluate a photoexcited proton transfer reaction pathway in comparison to classic carbene transfer reactions. (Figure presented.).
- Empel, Claire,Jana, Sripati,Koenigs, Rene M.,Verspeek, Dennis
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p. 4716 - 4722
(2020/09/23)
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- Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)-Catalyzed C?H Activation/Carbene Insertion/Lossen Rearrangement Sequence
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A rhodium(III)-catalyzed domino annulation of simple olefins with diazo oxindoles to give spirooxindole pyrrolone products is described. This reaction can be formally viewed as the result of an anomalous tandem C?H activation, carbene insertion, Lossen rearrangement, and a nucleophilic addition process. The potential utility of this reaction was further demonstrated by the late-stage diversification of drug molecules.
- Ma, Biao,Wu, Peng,Wang, Xing,Wang, Zhengyu,Lin, Hai-Xia,Dai, Hui-Xiong
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p. 13335 - 13339
(2019/08/20)
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- Copper(II)-Catalyzed Domino Synthesis of Indolo[3,2- c]quinolinones via Selective Carbonyl Migration
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A Cu(II)-catalyzed domino process involving the carbene N-H insertion, intramolecular aldol-type trapping and unprecedented ring-expansion of oxindole core through C3-selective 1,2-carbonyl migration is described for the synthesis of indolo[3,2-c]quinolinones. This tetracyclic core, having an all-carbon quaternary center, was efficiently synthesized in high yields from amines and 3-diazo-oxindoles. Mechanistic studies revealed that this reaction proceeds via a stepwise pathway and the involvement of the synergistic catalysis between Lewis acidic copper and hidden Br?nsted acidity of in-situ-formed TfOH traces.
- Arunprasath, Dhanarajan,Sekar, Govindasamy
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p. 867 - 871
(2019/05/16)
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- Chameleon-Like Activating Nature of the Spirooxindole Group in Donor-Acceptor Cyclopropanes
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The concept of a chameleon activating group is considered in the context of donor-acceptor cyclopropane chemistry. When spiro-conjugated with cyclopropane, oxindole can act as an acceptor or a donor depending on the electronic nature of vicinal substituents. This dichotomy is reflected in the alteration of chemoselectivity of spiro[oxindole-1,3′-cyclopropane] ring opening with nucleophiles.
- Akaev, Andrey A.,Melnikov, Mikhail Ya.,Budynina, Ekaterina M.
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p. 9795 - 9799
(2019/12/02)
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- Gold(I)-Catalyzed Dimerization of 3-Diazooxindoles towards Isoindigos
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A gold-catalyzed dimerization of 3-diazooxindoles was developed, delivering isoindigos as products. The reaction shows broad substrate scope and functional group tolerance by affording various substituted isoindigos. Moreover, the method also exhibited high efficiency on a gram-scale reaction.
- Yao, Xinbo,Wang, Tao,Zhang, Zunting
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supporting information
p. 4475 - 4478
(2018/09/06)
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- Nickel(II)-Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect
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A highly enantioselective [2,3] Wittig rearrangement of oxindole derivatives was realized by using a chiral N,N′-dioxide/NiII complex as the catalyst under mild reaction conditions. A strong chiral amplification effect was observed, and allowed access to chiral 3-hydroxy 3-substituted oxindoles bearing allenyl groups in high yields and enantioselectivities (up to 92 % ee) by using a ligand with only 15 % ee. A reasonable explanation was given based on the experimental investigations and X-ray crystal structures of enantiomerically pure and racemic catalysts. Moreover, the first catalytic kinetic resolution of racemic oxindole derivatives by a [2,3] Wittig rearrangement was realized with high efficiency and stereoselectivity.
- Xu, Xi,Zhang, Jianlin,Dong, Shunxi,Lin, Lili,Lin, Xiaobin,Liu, Xiaohua,Feng, Xiaoming
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p. 8734 - 8738
(2018/07/14)
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- Facile synthesis of 3-aryloxindoles via Bronsted acid catalyzed friedel-crafts alkylation of electron-rich arenes with 3-diazooxindoles
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A simple metal-free method for the synthesis of 3-aryloxindoles via Bronsted acid catalyzed aromatic C-H functionalization of electron-rich arenes with 3-diazooxindoles is developed. In the presence of a catalytic amount of TfOH, a series of 3-aryloxindoles are synthesized as single regioisomers in good to excellent yields. This transformation is proposed to proceed through acid-catalyzed protonation of 3-diazooxindoles into diazonium ions followed by Friedel-Crafts-type alkylation of arenes.
- Zhai, Changwei,Xing, Dong,Jing, Changcheng,Zhou, Jun,Wang, Chengjin,Wang, Dongwei,Hu, Wenhao
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p. 2934 - 2937
(2014/06/23)
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- One-Pot Tandem Diastereoselective and Enantioselective Synthesis of Functionalized Oxindole-Fused Spiropyrazolidine Frameworks
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A highly efficient palladium(0)-catalyzed asymmetric [3+2] cycloaddition using 3-diazooxindoles serving as dipolarophiles affords functionalized pyrazolidine derivatives in an atom-economical way. In addition, by trapping the pyrazolidine derivatives with maleimides, the corresponding spiropyrazolidine oxindoles containing multiple stereogenic centers have been obtained in high yields along with moderate to good levels of diastereoselectivity and enantioselectivity under mild conditions. Thus, a novel three-component one-pot tandem reaction has been developed.
- Mei, Liang-Yong,Tang, Xiang-Ying,Shi, Min
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p. 13136 - 13142
(2016/02/19)
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- Potassium N-iodo p-toluenesulfonamide (TsNIK, iodamine-T): A new reagent for the oxidation of hydrazones to diazo compounds
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A new reagent for the oxidation of hydrazones to diazo compounds is described. N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T) allows the preparation of α-diazoesters, α-diazoamides, α-diazoketones and α-diazophosphonates in good yield and in high purity after a simple extractive work-up. α-Diazoesters were also obtained in high yield from the corresponding ketones through a one-pot process of hydrazone formation/oxidation. Diazo compounds: N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T), readily prepared from p-toluenesulfonamide and iodine in aqueous KOH, is a new reagent for the oxidation of hydrazones to diazo compounds in good yields and high purity (see scheme).
- Nicolle, Simon M.,Moody, Christopher J.
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supporting information
p. 4420 - 4425
(2014/05/06)
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- Br?nsted acid/rhodium(II) cooperative catalytic asymmetric three-component aldol-type reaction for the synthesis of 3-amino oxindoles
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Cooperation is key! Chiral Br?nsted acid/rhodium(II) cooperative catalysis enabled an enantioselective three-component aldol-type reaction of 3-diazo oxindoles and anilines with glyoxylates to give highly functionalized and structurally diverse 3-amino oxindoles in high stereoselectivity (>20:1 d.r., 99 % ee; see scheme). Copyright
- Ren, Lei,Lian, Xiao-Lei,Gong, Liu-Zhu
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supporting information
p. 3315 - 3318
(2013/07/11)
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- Diastereoselective synthesis of β-Lactam-oxindole hybrids through a three-component reaction of azetidine-2,3-diones, α-diazo-oxindoles, and alcohols catalyzed by [Rh2(OAc)4]
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β-Lactam-oxindole hybrids have been synthesized in good yields in a one-pot procedure through efficient and stereoselective capture of an oxonium ylide with azetidine-2,3-diones. The reaction allows high to moderate control of stereoselectivity, depending on the 3-diazo-oxindole precursor and the hydroxylic compound used. Two new quaternary stereogenic centers were formed; the stereochemistry at the C-3 quaternary center was controlled by a bulky substituent at C-4, whereas the stereoselectivity in the adjacent second quaternary stereogenic center was controlled by the α-diazo-oxindole. The stereochemistry of both quaternary centers has been unambiguously assigned by single-crystal X-ray diffraction. Densely functionalized β-lactam-oxindole hybrids have been prepared in a one-pot, multicomponent reaction between azetidine-2,3-diones, α-diazo-oxindoles, and alcohols. Two new stereogenic centers were formed; the stereochemistry at the new C-3 quaternary center was controlled by a bulky substituent at C-4, whereas the second new stereogenic center was controlled by the α-diazo-oxindole.
- Alcaide, Benito,Almendros, Pedro,Aragoncillo, Cristina,Callejo, Ricardo,Ruiz, M. Pilar,Torres, M. Rosario
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p. 2359 - 2366
(2012/06/04)
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- New method for the preparation of 3-diazo-1,3-dihydroindol-2-ones
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A new method for the preparation of diazo compounds of 2-indolinone series by oxidation of isatin hydrazones with polyhaloalkanes in the presence of copper salts in catalytic amounts was developed.
- Muzalevskiy,Balenkova,Shastin,Magerramov,Shikhaliev,Nenajdenko
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p. 2343 - 2346
(2012/11/07)
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- Ring opening reaction of furan with high regio- and diastereo-selectivity via controlled addition of isatin-derived diazoamides
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Reaction of cyclic diazoamides with furan systems using rhodium(II) acetate as a catalyst afforded a variety of (3Z)-3-[(2E)-4-oxopent-2-en-1-ylidene] indol-2-ones in a regio- and diastereo-selective manner. The diastereoselectivity was based on the flow rate of cyclic diazoamides. The representative products were characterized by single-crystal X-ray analyses.
- Muthusamy, Sengodagounder,Azhagan, Datshanamoorthy
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p. 6732 - 6735
(2012/01/03)
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- Multicomponent reactions of diazoamides: Diastereoselective synthesis of mono- and bis-spirofurooxindoles
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This paper describes the intermolecular generation of carbonyl ylides by dirhodium(II) tetraacetatecatalyzed reaction of 3-diazoindol-2-ones in the presence of aryl aldehydes and heteroaryl aldehydes. These carbonyl ylides were subsequently trapped with dipolarophiles such as dimethyl acetylene- dicarboxylate, maleic anhydride, and ethyl acrylate to afford spirofurooxindoles. Consequently, diastereoselective synthesis of spirodihydrofurooxindoles through the multicomponent reactions of cyclic diazoamides was successfully achieved for the first time. The stereochemistry of the spirofurooxindole is unequivocally corroborated by the single-crystal X-ray analysis of the representative product 4o. Interestingly, these reactions were extended to double multicomponent reactions of bis-cyclic diazoamides to afford the respective complex polycycles in a tandem manner, which led to the construction of four carbon-carbon bonds, two carbon-oxygen bonds, and four chiral centers in a single synthetic step.
- Muthusamy, Sengodagounder,Gunanathan, Chidambaram,Nethaji, Munirathinam
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p. 5631 - 5637
(2007/10/03)
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- First example of regiospecific intermolecular C-H insertion reactions of cyclic rhodium carbenoids: Novel synthesis of 3-indol-3′-yloxindoles
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Facile regiospecific intermolecular C-H insertion reactions of cyclic rhodium carbenoids have been achieved using diazo carbonyl compounds 1 and indole or N-substituted indoles to afford 1,3-dihydro-1′H-[3,3′]biindolyl-2-ones, 3a-o in an excellent yield.
- Muthusamy, Sengodagounder,Gunanathan, Chidambaram,Babu, Srinivasarao Arulananda,Suresh, Eringathodi,Dastidar, Parthasarathi
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p. 824 - 825
(2007/10/03)
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