Computationally Assisted Mechanistic Investigation into Hypervalent Iodine Catalysis: Cyclization of N-Allylbenzamide DOI

Smaher E. Butt,

Mirdyul Das,

Jean‐Marc Sotiropoulos

et al.

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(23), P. 15605 - 15613

Published: Nov. 1, 2019

Previous experimental work identified 2-iodoanisole as the best precatalyst for oxidative cyclization of N-alkenylamides into 2-oxazolines. Herein, we describe our investigation effect on reaction rate based structure iodoarene precatalyst. We also reveal mechanism DFT modeling and obtain a clear correlation between observed rates computationally derived activation energies different iodoarenes. In addition, rate-limiting step is shown to be substrate that zero order in concentration The found correlate with ease oxidation iodoarene; however, most easily oxidized iodoarenes generate iodine(III) species decompose readily. Finally, loss from cyclized intermediate can proceed by either ligand-coupling or SN2 displacement (reductive elimination), this substrate-dependent.

Language: Английский

Metal-Free Synthesis of Benzimidazolinones via Oxidative Cyclization Under Hypervalent Iodine Catalysis DOI Creative Commons

Mayu Hirashima,

Syotaro Hamatani,

Hirotaka Sasa

et al.

Chemistry, Journal Year: 2025, Volume and Issue: 7(2), P. 50 - 50

Published: March 31, 2025

Benzimidazolinones exhibit unique biological activities and serve as building blocks in synthesizing pharmaceutical compounds. Although multiple synthetic approaches involving intermolecular cyclization reactions have been reported, intramolecular are scarce, more rational methods required. Hypervalent iodine-catalyzed oxidative C–N coupling is a potentially effective approach for benzimidazolinones under metal-free conditions. In this study, we present method utilizing hypervalent iodine catalysis the of N’-aryl urea compounds, resulting first synthesis various benzimidazolinones.

Language: Английский

Citations

0
Natural and Synthetic Spirobutenolides and Spirobutyrolactones DOI
Pratik Yadav, Ramendra Pratap,

Vishnu Ji Ram

et al.

Asian Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 9(10), P. 1377 - 1409

Published: Aug. 1, 2020

Abstract Spirobutenolides and spirobutyrolactones structural motifs are widespread in various natural products that exhibit a broad array of biological activities. Additionally, their synthetic analogues also serve as biologically active compounds building blocks complex molecules. Owing to the wide range pharmacological activities diversity spirobutenolides spirobutyrolactones, efficient methodologies have been established construct such interesting scaffolds. In past decades, numerous total syntheses containing reported. Structurally diverse synthesized by using singlet oxygen, Mannich reaction, aldol condensation, rearrangement Reformatsky Michael‐addition cyclization, Diels‐Alder photocyclization pericyclic reactions. Recently, metal‐catalyzed photocatalyzed radical Baylis‐Hillman asymmetric organocatalysis, NHC catalysis, ring contraction reactions, hypervalent iodine catalysis emerged powerful tools architect these nuclei. This review gives an overview advancements chemically relevant origin. It covers newer for construction well along with potential applications.

Language: Английский

Citations

28
Rapid Assembly of Spiroisoxazolidines by [4 + 1] Dearomative Spiroannulation of α-Bromo-β-naphthol and Nitroolefin DOI
Mian Qi, Mengyao Li, Lu Bai

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5997 - 6007

Published: April 10, 2023

A novel [4 + 1] dearomative spiroannulation of α-halo-β-naphthol and nitroolefin has been developed for the direct construction various spiroisoxazolidines in high chemo- diastereoselectivity. Notably, halophenols (X = Cl I) were also tolerated by this reaction. This transformation was realized through a sequence electrophilic dearomatization/dehalogenation, mechanistic studies revealed that different routes occurred C(sp3)-X bond cleavage. Moreover, potential application method exemplified several further transformations.

Language: Английский

Citations

10
Oxidative Reactions Mediated by Hypervalent Iodine Reagents DOI
Jiaxin He, Yunfei Du

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Mechanistic investigation into phenol oxidation by IBX elucidated by DFT calculations DOI
Amritpal Kaur, Alireza Ariafard

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(6), P. 1117 - 1129

Published: Jan. 1, 2020

Density functional theory (DFT) at the SMD/M06-2X/def2-TZVP//SMD/M06-2X/LANL2DZ(d),6-31G(d) level was used to explore regioselective double oxidation of phenols by a hypervalent iodine(v) reagent (IBX) give o-quinones.

Language: Английский

Citations

26
Controlled Synthesis of One-Handed Helical Polymers Carrying Achiral Organoiodine Pendants for Enantioselective Synthesis of Quaternary All-Carbon Stereogenic Centers DOI

Xue Song,

Yan‐Xiang Li, Li Zhou

et al.

Macromolecules, Journal Year: 2022, Volume and Issue: 55(11), P. 4441 - 4449

Published: June 6, 2022

Inspired by highly efficient and enantioselective reactions catalyzed biomacromolecules, developing artificial helical polymer-based catalysts for is an interesting work. In this work, a series of one-handed polyisocyanides bearing aryl iodine pendants were readily produced via asymmetric polymerization achiral isocyanides using chiral Pd(II)-catalysts. Despite the inexistence any stereogenic centers, these polymers showed large optical activity owing to helicity. Remarkably, could catalyze dearomatization spirocyclization 1-hydroxy-N-aryl-2-naphthamide derivatives gave spirooxindole products with high enantioselectivity. The enantioselectivity was contributed helicity polyisocyanide backbone; in opposite enantiomeric antipode comparable yields similar Thanks molecular weight, polymer be recycled 10 times maintained stereoselectivity.

Language: Английский

Citations

16
An Efficient Approach for 3,3-Disubstituted Oxindoles Synthesis: Aryl Iodine Catalyzed Intramolecular C–N Bond Oxidative Cross-Coupling DOI
Yang Wang,

Mo Yang,

Yuanyuan Sun

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(22), P. 8750 - 8754

Published: Oct. 28, 2021

Herein, we report the first intramolecular C-N bond formation of phenylpropanamide derivatives via organocatalytic oxidative reactions, affording 3,3-disubstituted oxindole with up to 99% yield. The high efficiency this reaction is exemplified by transition metal-free mild conditions and ability perform on a gram scale. Meanwhile, DFT calculation catalytic transformation pathway has also been studied.

Language: Английский

Citations

18
Recent advances in catalytic oxidative reactions of phenols and naphthalenols DOI
Muhammad Adnan Bashir, Jian Wei, Huifei Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(19), P. 5395 - 5413

Published: Jan. 1, 2022

This critical review aims to provide an overview of oxidative phenol and naphthalenol transformations in nature synthetic chemistry.

Language: Английский

Citations

14
Mechanism of Iodine(III)‐Promoted Oxidative Dearomatizing Hydroxylation of Phenols: Evidence for a Radical‐Chain Pathway DOI

Karol Kraszewski,

Ireneusz Tomczyk, Aneta Drabińska

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(50), P. 11584 - 11592

Published: July 1, 2020

Abstract The oxidative dearomatization of phenols with the addition nucleophiles to aromatic ring induced by hypervalent iodine(III) reagents and catalysts has emerged as a highly useful synthetic approach. However, experimental mechanistic studies this important process have been extremely scarce. In report, we describe systematic investigations dearomatizing hydroxylation using an array techniques. Kinetics, EPR spectroscopy, reactions radical probes demonstrate that transformation proceeds radical‐chain mechanism, phenoxyl being key chain‐carrying intermediate. Moreover, UV NMR high‐resolution mass spectrometry, cyclic voltammetry show before reacting radical, water molecule becomes activated interaction center, causing Umpolung formally nucleophilic substrate. mechanism allows rationalization all existing observations regarding iodine(III)‐promoted phenols.

Language: Английский

Citations

19
Innovation of hypervalent(iii) iodine in the synthesis of natural products DOI
Zhuo Wang

New Journal of Chemistry, Journal Year: 2020, Volume and Issue: 45(2), P. 509 - 516

Published: Dec. 24, 2020

The focus article discusses the innovation of hypervalent(iii) iodine regarding skeletal rearrangement, cycloaddition and cyclization, sp3 C–H functionalization in natural product synthesis.

Language: Английский

Citations

19