Organocatalytic Asymmetric Michael Reactions of Cyclic N-Sulfonylimines with Nitroalkenes or 2-Nitroallylic Acetates

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

A highly efficient enantioselective Michael addition of cyclic N-sulfonylimines with nitroalkenes has been developed, utilizing a bifunctional squaramide catalyst. This approach achieves remarkable results, delivering products high yields and outstanding stereoselectivities, reaching up to 97% yield, >20:1 dr, >99% ee. Furthermore, an asymmetric tandem reaction 2-nitroallylic acetates established. innovative methodology involves Michael/intramolecular aza-Michael cascade, leading the formation enantioenriched benzosultam-fused tricyclic compounds excellent stereoselectivities (up dr ee).

Language: Английский

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Organo/Silver Dual Catalytic (3 + 2)/Conia-Ene Type Cyclization: Asymmetric Synthesis of Indane-Fused Spirocyclopenteneoxindoles

Organic Letters, Journal Year: 2022, Volume and Issue: 24(33), P. 6197 - 6201

Published: Aug. 17, 2022

Developing efficient strategies to synthesize spirocyclopenteneoxindoles is an attractive target due their potential biological activity. This work described the thiourea/silver dual catalytic (3 + 2)/Conia-ene type reaction of 2-(2-oxoindolin-3-yl)malononitrile with ortho-ethynyl substituted nitrostyrene. The features mild conditions and good atom- step-economy. Three new C–C bonds were formed within one synthetic step, providing indane-fused in yields, excellent chemo-, regio-, stereoselectivity.

Language: Английский

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Recent advances in the synthetic applications of Morita–Baylis–Hillman and Rauhut–Currier adducts of nitroalkenes

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(31), P. 6243 - 6262

Published: Jan. 1, 2023

This article reviews the recent applications of Morita–Baylis–Hillman and Rauhut–Currier adducts nitroalkenes. It also covers mechanistic aspects, including key intermediates reaction pathways.

Language: Английский

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Stereocontrolled Construction of Spirooxindole-Containing 5,6,7,8-Tetrahydropyrrolo[1,2-a]pyridine via Michael/Friedel–Crafts Domino Reaction Promoted by Secondary Amine-Squaramide

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2152 - 2157

Published: March 8, 2024

An asymmetric Michael/Friedel–Crafts cascade reaction with Morita–Baylis–Hillman (MBH) nitroallylic esters and 3-pyrrolyloxindoles has been developed for the stereoselective construction of spirooxindole-containing tetrahydroindolizines. A range tetracyclic scaffolds possessing three consecutive chiral centers, including an all-carbon quaternary stereocenter, were generated in 53–85% isolated yields high diastereoselectivities enantiopurities (≥3:1 dr, 50–98% ee). newly synthesized bifunctional secondary amine/squaramide organocatalyst was demonstrated to exhibit better stereochemical control than their tertiary analogues.

Language: Английский

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One‐Pot Regio‐ and Diastereoselective Synthesis of Tetrahydro‐α‐carbolines via Cascade Reactions of Iminoindolines with Morita‐Baylis‐Hillman Bromides of Nitroalkenes

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2022(3)

Published: Dec. 24, 2021

Abstract A mild and metal‐free method for the one‐pot synthesis of highly substituted tetrahydro‐ α ‐carbolines from Morita‐Baylis‐Hillman (MBH) bromides nitroalkenes iminoindolines has been demonstrated. Cascade reaction MBH with tosyliminoindolines occurs regio‐ as well diastereoselectivity in a formal [3+3] manner to form various wide substrate scope under conditions. All products were obtained high yields within short time. Also, synthetic efficiency methodology was demonstrated by gram scale experiment further converting them into 3‐nitro‐ ‐carbolines.

Language: Английский

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Kinetic Studies of Hantzsch Ester and Dihydrogen Donors Releasing Two Hydrogen Atoms in Acetonitrile

ACS Omega, Journal Year: 2022, Volume and Issue: 7(30), P. 26416 - 26424

Published: July 22, 2022

In this work, kinetic studies on HEH2, 2-benzylmalononitrile, 2-benzyl-1H-indene-1,3(2H)-dione, 5-benzyl-2,2-dimethyl-1,3-dioxane-4,6-dione, 5-benzyl-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione, 2-(9H-fluoren-9-yl)malononitrile, ethyl 2-cyano-2-(9H-fluoren-9-yl)acetate, diethyl 2-(9H-fluoren-9-yl)malonate, and the derivatives (28 XH2) releasing two hydrogen atoms were carried out. The thermokinetic parameters ΔG⧧° of 28 dihydrogen donors (XH2) corresponding atom acceptors (XH•) in acetonitrile at 298 K determined. abilities for these organic researched using their ΔG⧧°(XH2), which can be used not only to compare H-donating ability different XH2 qualitatively quantitatively but also predict rates HAT reactions. Predictions rate constants 12 reactions determined, reliabilities predicted results examined.

Language: Английский

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[3+2]-Annulation of oxindolinyl-malononitriles with Morita–Baylis–Hillman acetates of nitroalkenes for the regio- and diastereoselective synthesis of spirocyclopentane-indolinones

Tetrahedron, Journal Year: 2022, Volume and Issue: 108, P. 132650 - 132650

Published: Jan. 13, 2022

Language: Английский

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Design, Synthesis, and Biological Evaluation of Tetrahydro‐α‐carbolines as Akt1 Inhibitors That Inhibit Colorectal Cancer Cell Proliferation

ChemMedChem, Journal Year: 2022, Volume and Issue: 17(11)

Published: March 31, 2022

A series of densely functionalized THαCs were designed and synthesized as Akt1 inhibitors. Organocatalytic [3+3] annulation between indolin-2-imines 1 nitroallylic acetates 2 provided rapid access to this pharmacologically interesting framework. In vitro kinase inhibitory abilities cytotoxicity assays revealed that compound 3 af [(3S*,4S*)-4-(4-bromo-2-fluorophenyl)-9-methyl-3-nitro-1-tosyl-2,3,4,9-tetrahydro-1H-pyrido[2,3-b]indole] was the most potent inhibitor, mechanistic study indicated suppressed proliferation colorectal cancer cells via inducing apoptosis autophagy. Molecular docking suggested indole fragment inserted into hydrophobic pocket protein, H-bond residue Lys179 also contributed stable binding. This article provides an efficient strategy design synthesize biologically important compounds novel

Language: Английский

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[3+2] Cycloaddition Reactions of 2‐Ylidene Acenaphthylenones with 3‐Benzylidene Succinimides and 1,4‐Benzoxazinone Derivatives

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(12)

Published: Oct. 24, 2022

Abstract A base‐catalyzed novel [3+2] cycloaddition reaction between arylidene‐1‐phenyl succinimides and alkylidene acenaphthylenones is carried out to access succinimide substituted spiro[acenaphthylenone‐cyclopentane]fused scaffolds with high regio‐ stereo‐selectivity under mild conditions. The of 1,4‐benzoxazinone derivatives the influence environmentally benign iodine afforded polyheterocyclic compounds embedded pyrrole moiety. This metal‐free synthesis highly efficient atom economic protocol obviates column chromatography. products are isolated by simple decantation followed washing solvent.

Language: Английский

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Highly diastereoselective [3+3] cycloaddition of indolin-3-ones and nitroallylic acetates: Efficient access to polysubstituted dihydropyrano[3,2-b]indoles

Tetrahedron, Journal Year: 2023, Volume and Issue: 133, P. 133275 - 133275

Published: Jan. 20, 2023

Language: Английский

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