- Organocatalytic Enantioselective Synthesis of Tetrahydro-Furanyl Spirooxindoles via [3+2] Annulations of 3-Hydroxyoxindoles and Cyclic Ketolactams
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Asymmetric construction of pharmacologically interesting tetrahydrofuranyl spirooxindole frameworks has been achieved through organocatalytic [3+2] annulations of the readily available 3-hydroxyoxindoles and pyrrolidone-derived cyclic ketolactams. A variety of chiral spiro tetrahydrofuranyl products, which contain four contiguous stereocenters including two tetrasubstituted carbon centers, have been rapidly synthesized with remarkable results (up to 99% yield, >95:5 dr, and 99:1 er). Synthetic derivatization of the hemiketal moiety enables the installation of various halogen atoms into the structurally complex molecules in a stereospecific manner. Preliminary screening of anticancer bioactivity was performed, and 4 w showed obvious inhibitory capacity to the proliferation on a panel of cancer cell lines. (Figure presented.).
- Liu, Yue,Zhang, Ying,Huang, Qian-Wei,Gou, Chuan,Li, Qing-Zhu,Dai, Qing-Song,Leng, Hai-Jun,Li, Jun-Long
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p. 2177 - 2182
(2021/03/08)
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- Oxindole spiro-tetrahydrofuran compound as well as preparation method and application thereof
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The invention provides an indole tetrahydrofuran oxide compound or a crystal form thereof, wherein the indole tetrahydrofuran oxide compound is as shown in a formula (I). R1 is selected from benzene rings, naphthalene rings and thiophene rings or cinnamyl, R2 is selected from H, F, Cl, Br and I or C1-3 alkoxy, R3 is selected from H and benzyl or C1-C3 alkyl, and R4 is H, F, Cl, Br, I and C1-3 alkoxy or C1-C3 alkyl. The invention further provides a method for preparing the compound. The compound is simple and convenient in preparation method, moderate in reaction and high in yield and has anti-tumor activity and a wide market application prospect.
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- 3-Hydroxy-3-((3-methyl-4-nitroisoxazol-5-yl)methyl)indolin-2-one as a versatile intermediate for retro-Henry and Friedel-Crafts alkylation reactions in aqueous medium
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The first example of a retro-Henry type reaction is reported using 3-hydroxy-3-((3-methyl-4-nitroisoxazol-5-yl)methyl)indolin-2-ones which are prepared via catalyst-free Henry reaction of 3,5-dimethyl-4-nitroisoxazole and isatin. These compounds were used
- Nagaraju, Sakkani,Sathish, Kota,Paplal, Banoth,Satyanarayana, Neeli,Kashinath, Dhurke
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p. 14045 - 14050
(2019/09/18)
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- Domino Grignard Addition and Oxidation for the One-Pot Synthesis of C2-Quaternary 2-Hydroxyindoxyls
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We herein delineate an unexplored reactivity of 3-hydroxyoxindoles toward Grignard addition enabling a rapid access to a broad range of unnatural C2-quaternary 2-hydroxyindoxyls in high yields. The reaction proceeds via a mechanistically intriguing one-pot 1,2-hydride shift followed by autoxidation pathway. The utility of this method is demonstrated by the synthesis of a new class of bis-indoxyl spirofuran derivatives.
- Mandal, Tirtha,Chakraborti, Gargi,Maiti, Subhadip,Dash, Jyotirmayee
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supporting information
p. 8044 - 8048
(2019/10/11)
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- Oxoindole spiral tetrahydrofuran framework and its crystal and preparation method
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The invention discloses an oxoindole spiral tetrahydrofuran framework and its preparation method. The structural formula is shown as Formula I. The invention further discloses a crystal form of the compound shown in Formula I; the crystal form is a monoclinic system, the cell parameter alpha is equal to 90 degrees, beta is equal to 94.278(3) degrees, and gamma is equal to 90 degrees; the space group is P21, Z=2; the cell volume is shown as specification. The invention further discloses a preparation method of the crystal form, and also discloses an application of the compound, or its crystal form, or its solvent compound, or pharmaceutically acceptable salts in preparation of anti-cancer drugs.
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- Oxoindolespiro tetrahydrofuran fluoride, crystal, preparation method and application thereof
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The invention discloses oxoindolespiro tetrahydrofuran fluoride and a preparation method thereof. The structural formula of oxoindolespiro tetrahydrofuran fluoride is shown as formula I. The inventionfurther discloses a crystal form of a compound shown as the formula I, the crystal form is a monoclinic system, cell parameters include that a=9.09964(19) angstrom, b=9.3177(3) angstrom, c=15.6040(4)angstrom, alpha is equal to 90 degrees, beta is equal to 99.228 (2) degrees, and gamma is equal to 90 degrees; space group is P21, Z=2, and cell volume is 1305.91(6) angstrom. The invention further discloses a preparation method of the crystal form, the compound or the crystal form thereof or a solvate thereof or application of pharmaceutically acceptable salt thereof in preparing antitumor drug.
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- Iridium-Catalyzed Enantioselective and Diastereoselective Allylation of Dioxindoles: A One-Step Synthesis of 3-Allyl-3-hydroxyoxindoles
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An iridium-catalyzed asymmetric allylation of dioxindoles, 3-hydroxyoxindoles, regulated by prosthetic groups has been accomplished under mild conditions. The methodology is applicable to a diverse array of 3-hydroxyoxindole and cinnamyl acetate substrates. A range of 3-allyl-3-hydroxyoxindoles containing vicinal tetrasubstituted and trisubstituted stereocenters can be efficiently synthesized in one-step with excellent enantioselectivity (up to >99% enaniomeric excess (ee)) and good diastereoselectivity (up to 11:1 diastereomeric ratio (dr)).
- He, Rui,Wu, Shanchao,Tang, Haoming,Huo, Xiaohong,Sun, Zhenliang,Zhang, Wanbin
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p. 6183 - 6187
(2018/10/02)
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- Indium-mediated Palladium-catalyzed Allylic Alkylation of Isatins with Alkynes
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An unprecedented indium-mediated palladium-catalyzed allylic alkylation of isatins with alkynes is disclosed. This reaction provides a new, practical, and straightforward route to access 3-allyl-3-hydroxy-2-oxindoles in good yields with broad substrate scope and scalability, exhibiting high atom and step economy. A primary mechanistic study reveals that indium played two roles in the reaction, first as a reductant and second as a Lewis acid. Compared with previous methods, our strategy eliminated the steps for the separation and purification of the reaction intermediates, as well as pre-installing leaving groups to allylic substrates. Moreover, our reaction did not employ moisture-sensitive allylic metal species and stoichiometric oxidants. (Figure presented.).
- Wu, Zijun,Fang, Xinxin,Leng, Yuning,Yao, Hequan,Lin, Aijun
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p. 1289 - 1295
(2018/02/21)
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- The Power of Triplet and Singlet Oxygen in Synthesis: 2-Oxindoles, 3-Hydroxy-2-oxindoles, and Isatins from Furans
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A straightforward synthesis of substituted 2-oxindoles, 3-hydroxy-2-oxindoles, and isatins has been developed. Easily accessible furans were transformed into tetrahydropyranopyrrolones by a singlet oxygen initiated cascade reaction sequence. An acid-catal
- Triantafyllakis, Myron,Sfakianaki, Kalliopi,Kalaitzakis, Dimitris,Vassilikogiannakis, Georgios
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supporting information
p. 3631 - 3634
(2018/06/26)
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- Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel-Catalyzed Transfer-Hydrogenative Strategy
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Nickel-catalyzed coupling of benzyl acrylates with activated ketones and imines provides γ-butyrolactones and lactams, respectively. The benzyl alcohol byproduct released during the lactonization/lactamization event is relayed to the next cycle where it serves as the reductant for C?C bond formation. This strategy represents a conceptually unique approach to transfer-hydrogenative C?C bond formation, thus providing examples of reductive heterocyclizations where hydrogen embedded within an alcohol leaving group facilitates turnover.
- Buxton, Craig S.,Blakemore, David C.,Bower, John F.
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p. 13824 - 13828
(2017/10/24)
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- Squaramide-Catalyzed Enantioselective Cascade Approach to Bispirooxindoles with Multiple Stereocenters
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A bifunctional squaramide-catalyzed Michael/Michael cascade reaction for the construction of spirotetrahydrofuran bispirooxindoles was developed. The products were obtained in moderate to excellent yields with excellent diastereo- and enantioselectivities
- Zhao, Bo-Liang,Du, Da-Ming
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p. 3992 - 3998
(2016/12/30)
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- Palladium catalyzed asymmetric allylation of 3-OBoc-Oxindoles: An efficient synthesis of 3-Allyl-3-hydroxyoxindoles
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3-Allyl-3-hydroxyoxindoles were synthesized in very good enantio- (up to 97% ee) and diastereoselectivities (dr up to 7.6:1) with contiguous quaternary and tertiary stereogenic centers by employing tartrate derived bi(oxazoline) in Pd-catalyzed allylation of 3-OBoc-oxindole. Synthetic utility of 3-allyl-3-hydroxyoxindole was demonstrated by synthesizing a highly substituted spiro(oxindole-3,2′-tetrahydrofuran) derivative in good yield and stereoselectivity.
- Jayakumar, Samydurai,Kumarswamyreddy, Nandarapu,Prakash, Muthuraj,Kesavan, Venkitasamy
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supporting information
p. 1066 - 1069
(2015/03/18)
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- Enantioselective synthesis of spirooxindole α-exo-methylene-γ- butyrolactones from 3-OBoc-oxindoles
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Chiral Lewis bases facilitated the synthesis of highly functionalized spirooxindoles containing α-exo-methylene-γ-butyrolactones in high yields (76-92 %) and excellent enantioselectivities (up to 98 % ee) at ambient temperature.
- Jayakumar, Samydurai,Muthusamy, Subramaniam,Prakash, Muthuraj,Kesavan, Venkitasamy
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supporting information
p. 1893 - 1898
(2014/04/03)
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- Enantioselective Synthesis of Spirooxindole α-exo-Methylene-γ-butyrolactones from 3-OBoc-Oxindoles
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Chiral Lewis bases facilitated the synthesis of highly functionalized spirooxindoles containing α-exo-methylene-γ-butyrolactones in high yields (76-92 %) and excellent enantioselectivities (up to 98 % ee) at ambient temperature.
- Jayakumar, Samydurai,Muthusamy, Subramaniam,Prakash, Muthuraj,Kesavan, Venkitasamy
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supporting information
p. 1893 - 1898
(2015/10/05)
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- Controlling the molecular topology of vinylogous iminium ions by logical substrate design: Highly regio- and stereoselective aminocatalytic 1,6-addition to linear 2,4-dienals
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All about topology control: The title reaction yields valuable tetrahydrofuran spirooxindoles (see scheme; TMS=trimethylsilyl), and exemplifies a rare asymmetric 1,6-addition to linear 2,4-dienals proceeding with high δ-site- and stereoselectivity. A steering group at the β-dienal position ensured molecular preorganization of the catalytically active vinylogous iminium ion intermediate for highly predictable reaction outcomes. Copyright
- Silvi, Mattia,Chatterjee, Indranil,Liu, Yiankai,Melchiorre, Paolo
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p. 10780 - 10783
(2013/10/22)
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- Regioselective ruthenium catalyzed hydrohydroxyalkylation of dienes with 3-hydroxy-2-oxindoles: Prenylation, geranylation, and beyond
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The direct conversion of secondary to tertiary alcohols via ruthenium(0) catalyzed C-C coupling of substituted 3-hydroxy-2-oxindoles with various dienes is described. Coupling occurs in a completely regioselective manner in the absence of stoichiometric b
- Chen, Te-Yu,Krische, Michael J.
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supporting information
p. 2994 - 2997
(2013/07/26)
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- Dioxindole in asymmetric catalytic synthesis: Direct access to 3-substituted 3-hydroxy-2-oxindoles via 1,4-additions to nitroalkenes
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The asymmetric Michael addition of dioxindoles to β-substituted nitroalkenes is reported. The bifunctional primary amine-thiourea A, by means of a non-covalent-based mode of catalysis, secures direct access to 3-substituted 3-hydroxyoxindole derivatives with high stereocontrol. The Royal Society of Chemistry 2012.
- Retini, Michele,Bergonzini, Giulia,Melchiorre, Paolo
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p. 3336 - 3338
(2012/04/17)
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- Dinuclear zinc catalyzed asymmetric spirannulation reaction: An umpolung strategy for formation of α-alkylated-α-hydroxyoxindoles
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A highly diastereo- and enantioselective formal [3 + 2] cycloaddition of α,β-unsaturated esters and 3-hydroxyoxindoles catalyzed by a dinuclear zinc-ProPhenol complex is reported. The stereoselective Michael additions of 3-hydroxyoxindoles and the subsequent transesterifications afford spirocyclic δ-lactones.
- Trost, Barry M.,Hirano, Keiichi
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supporting information; experimental part
p. 2446 - 2449
(2012/07/27)
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- Dioxindole in asymmetric catalytic synthesis: Routes to enantioenriched 3-substituted 3-hydroxyoxindoles and the preparation of maremycin A
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Taming the reactivity: Understanding the nucleophilicity of dioxindole under different reaction conditions is key to a direct and easy access to valuable spiro oxindole ? butyrolactones and 3-substituted 3-hydroxyoxindole derivatives in excellent yields and enantioselectivities (see scheme). The preparation of maremycin A serves as an example for the potential usefulness of this previously unexplored reactivity in natural product synthesis. Copyright
- Bergonzini, Giulia,Melchiorre, Paolo
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supporting information; experimental part
p. 971 - 974
(2012/03/08)
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