Preparation of spiro[cyclopropane-1,3'-(3H)-indol]ones from isatin in a novel one-step process. A study of long-range chiral recognition

Eberle, Marcel K.; KAHLE, G. G.; Shapiro, Michael J.

doi:10.1021/jo00132a051

Cited by 21 publications

(10 citation statements)

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“…The initial addition of isatin to ylide generated the alkenyl intermediate 7 which upon reaction with another molecule of ylide 12 furnished the spirocyclopropyl ring 1 . [ 14 ]…”

Section: Synthesis Of Spirocyclopropyl Oxindolesmentioning

confidence: 99%

Syntheses and Applications of Spirocyclopropyl Oxindoles: A Decade Review

2020

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Spirocyclopropyl oxindole represents an emerging framework by unique amalgamation of versatile 2‐oxindole motif and highly strained cyclopropane unit. This scaffold is remarkable for its diverse medicinal and synthetic applications. The present review delivers a comprehensive overview of the strategies to afford spirocyclopropyl oxindoles and their potential synthetic transformations. The syntheses of spirocyclopropyl oxindoles have been described based on the type of precursors, including isatin, 3‐alkenyl oxindole, diazooxindole, oxindole, and 3‐chlorooxindole. Besides, the utility of different cyclopropanation reagents like sulfur ylide, MBH‐carbonate, carbenoid, vinyl selenone, etc. have also been emphasized. Furthermore, various ring‐expansion/opening reactions of spirocyclopropane oxindoles using dipolarophiles/nucleophiles have critically been illustrated.

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“…The initial addition of isatin to ylide generated the alkenyl intermediate 7 which upon reaction with another molecule of ylide 12 furnished the spirocyclopropyl ring 1 . [ 14 ]…”

Section: Synthesis Of Spirocyclopropyl Oxindolesmentioning

confidence: 99%

Syntheses and Applications of Spirocyclopropyl Oxindoles: A Decade Review

2020

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“…32 Morita−Baylis−Hillman adducts, 33 carbonates, and carbenoids were widely used as cyclopropanation reagents. Since the pioneering work of Eberle in 1982, 34 sulfoxonium and sulfur ylides were also used in the cyclopropanation reaction of 3-alkenyl oxindole or isatin in the synthesis of the spirocyclopropyl oxindole compounds. Han et al demonstrated that 3-alkenyl oxindoles bearing various functionalities exhibited high reactivity in the cyclopropanation of sulfoxonium ylides, even without a catalyst.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Morita–Baylis–Hillman adducts, carbonates, and carbenoids were widely used as cyclopropanation reagents. Since the pioneering work of Eberle in 1982, sulfoxonium and sulfur ylides were also used in the cyclopropanation reaction of 3-alkenyl oxindole or isatin in the synthesis of the spiro-cyclopropyl oxindole compounds. Han et al.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Selectivity of Cyclopropanation of 3-Alkenyl-oxindoles with Sulfoxonium Ylides Catalyzed by a Chiral N,N′-Dioxide–Mg(II) Complex

Meng

Wang

et al. 2021

J. Org. Chem.

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The mechanism and stereoselectivity of an asymmetric cyclopropanation reaction between 3-alkenyl-oxindole and sulfoxonium ylide catalyzed by a chiral N,N′dioxide−Mg(II) complex were explored using the B3LYP-D3(BJ) functional and the def2-TZVP basis set. The noncatalytic reaction occurred via a stepwise mechanism, with activation barriers of 21.6−23.5 kcal mol −1 . The C 2 −C α bond formed followed by the carbanion S N 2 substitution, constructing a three-membered ring in spiro-cyclopropyl oxindoles, accompanied by the release of dimethylsulfoxide. The electron-withdrawing Nprotecting t-butyloxy carbonyl (Boc) and acetyl (Ac) groups in isatin enhanced the local electrophilicity of the C2 atom and the repulsion between the two COPh groups in the reactants, contributing to high reactivity as well as good diastereoselectivity results. The N-Boc-3-phenacylideneoxindole coordinated to the chiral ligand (L-PiPr 2 ) in a bidentate fashion, forming a hexacoordinate-Mg(II) complex as the reactive species. The origin of enantioselectivity was from the shielding effect of 2,6-diisopropylphenyl groups in the ligand toward the si-face of oxindole. The repulsion between the SO(CH 3 ) 2 and COPh groups in 3-alkenyl-oxindole and the neighboring ortho-iPr group in the ligand directed the re-face of ylide to attack the re-face of oxindole preferably, contributing to the high diastereoselectivity of the product. A metal-ion−ligand matching relationship was important for a good asymmetric induction effect of the chiral N,N′-dioxide−metal catalyst. A large chiral cavity in the Zn(II) catalyst weakened the shielding effect of 2,6-diisopropylphenyl groups in the ligand toward the prochiral face of oxindole, leading to inferior enantioselectivity observed in the experiment.

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“…[15 -17] Reaction between 3-chlorooxindole and α,β-unsaturated olefins has been provided an operationally simple, stepwise pathway to construct functionalized spirocyclopropyl oxindoles. [18 -20] The cycloaddition of arsonium, [21] sulfonium, [22] phosphrous [23] and ammonium ylides [24] with electrondeficient olefins has been attempted by many researchers for the synthesis of cyclopropane-containing frameworks. Although this strategy provides highly diverse spirocyclic cyclopropanes, but suffer from formation of byproducts such as furan derivatives and often harsh reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective Sonochemical Synthesis of Spirocyclopropaneoxindoles and Evaluation of Their Antioxidant and Cytotoxic Activities

Pourshab

Asghari

Tajbakhsh

et al. 2019

Chemistry & Biodiversity

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An efficient diastereoselective synthesis of spirocyclopropaneoxindoles is reported using three‐component reactions of various phenacylidenetriphenylphosphorane, isatins and phenacyl bromide under ultrasonic irradiation. The structures of synthesized spirocyclopropaneoxindoles were characterized by their spectral data. The antioxidant activities of the synthesized compounds were evaluated by 1,1‐diphenyl‐2‐picrylhydrazyl radical scavenging assay. Among the products, those with NH group in their structure exhibited higher antioxidant activities than other derivatives. Also, in vitro cytotoxicity of compounds 4b, 4e, 4j, 4k were examined against heLa cancer cell lines using MTT assay. The results revealed that compound 4j with chlorine substituent on phenyl group displayed higher cytotoxicity activity (IC50=4.50±0.30 μg/mL) after 48 h.

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Preparation of spiro[cyclopropane-1,3'-(3H)-indol]ones from isatin in a novel one-step process. A study of long-range chiral recognition

Cited by 21 publications

References 0 publications

Syntheses and Applications of Spirocyclopropyl Oxindoles: A Decade Review

Syntheses and Applications of Spirocyclopropyl Oxindoles: A Decade Review

Mechanism and Selectivity of Cyclopropanation of 3-Alkenyl-oxindoles with Sulfoxonium Ylides Catalyzed by a Chiral N,N′-Dioxide–Mg(II) Complex

Diastereoselective Sonochemical Synthesis of Spirocyclopropaneoxindoles and Evaluation of Their Antioxidant and Cytotoxic Activities

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