Synthesis of new alkenyl iodobenzoate derivatives via Kharasch-Sosnovsky reaction using tert-butyl iodo benzoperoxoate and copper (I) iodide

Samadi, Saadi; Ashouri, Akram; Majidian, Shiva; Rashid, Hersh I

doi:10.1007/s12039-020-01852-8

Cited by 6 publications

(2 citation statements)

References 42 publications

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“…Column chromatography of the obtained residue on silica gel afforded (S)-2-cyclohexenyl-p-nitrobenzoate as a white solid (98%, 93% ee). The bisoxazoline ligand was also recovered in 92% yield 15,18,[50][51][52][76][77][78][79][80] .…”

Section: Methodsmentioning

confidence: 99%

Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch–Sosnovsky reaction

Samadi

Arvinnezhad

Mansoori

et al. 2022

Sci Rep

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Effect of a range of t-butyl perbenzoates bearing electron-withdrawing and electron-donating substitutions on the phenyl ring and HZSM-5 as a porous additive at 0 °C in enantioselective allylic C–H bond oxidation of cyclic and acyclic olefins in the presence of Cu (I)-(S,aS,S) complexes of biphenyl bisoxazoline ligands, produced easily through the chelation-induced process, were investigated. The enantioenriched allylic esters were obtained in reasonable times with excellent enantioselectivities and yields using electron-withdrawing substituted peresters in the presence of Cu (I)-(S,aS,S)-1a complex, containing phenyl groups at the stereogenic centers of the oxazoline moieties. To reach a better insight on geometry, chemical activity, enantioselectivity, and thermodynamic stability of the Cu (I)-BOX complexes, DFT calculations with B3LYP-D3/6-31G (d, p) level of theory were applied to them. Moreover, NBO analysis was used to illustrate interactions between orbitals.

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Section: Methodsmentioning

confidence: 99%

Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch–Sosnovsky reaction

Samadi

Arvinnezhad

Mansoori

et al. 2022

Sci Rep

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“…Since the allylic oxidation reaction (Kharasch–Sosnovsky reaction) products in the chiral form, chiral allylic esters and chiral allylic alcohols, play an important role as key intermediates for the total synthesis of a variety of natural products and biologically significant compounds, this reaction has garnered the attention of numerous chemists. − Therefore, an important part of allylic oxidation reactions is the development of effectual chiral catalysts. − Herein, chiral PHCs as an interesting category of chiral catalysts with unique characteristics were prepared, and after in situ immobilization of copper salts on them, they were used in the enantioselective allylic C–H bond oxidation of alkenes in the presence of different peresters in order to prepare chiral allylic esters (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Chiral Pseudohomogeneous Catalyst Based on Amphiphilic Carbon Quantum Dots for the Enantioselective Kharasch–Sosnovsky Reaction

Rezaei,

Zheng,

Majidian

et al. 2023

ACS Appl. Mater. Interfaces

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The term “chiral pseudohomogeneous catalyst (PHC)” denotes a novel concept that characterizes subnanometric particles exhibiting atomic-level chirality. The PHC based on chiral amphiphilic carbon quantum dots possesses distinctive features that combine the strengths of both homogeneous and heterogeneous catalysts, thereby heralding a significant breakthrough in the fields of asymmetric synthesis and medicinal chemistry. To the best of our knowledge, this is the first and the only reported research of a chiral PHC that demonstrates exceptional performance in controlling the enantioselectivity of the Kharasch–Sosnovsky reaction, yielding the corresponding products in high conversion (95%) with a moderate enantiomeric excess (75%). Notably, the chiral information on l-tryptophan can be effectively transferred from the outer shell of the nanosized catalyst, thereby inducing enantioselectivity in C–H activation and subsequent C–O forming events. Additionally, we have investigated the impact of various factors on the allylic oxidation reaction, including the amount, diversity, and hydrophilic/hydrophobic nature of the catalyst, as well as the influence of the solvent, Cu salts, temperature, and the type of alkene and perester, in order to comprehensively explore the reaction conditions. Furthermore, the catalyst can be readily recycled from the reaction medium, making this PHC a promising innovation that can significantly impact practical applications. In summary, this breakthrough can be aptly described as a “Golden Gate” due to its unparalleled potential to open up novel avenues for research and innovation.

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Copper‐Catalyzed Simultaneous Dehydrogenation and Enantioselective Allylic Oxidation of Alkanes Using Chiral Heterogeneous Ligands to Produce Allylic Esters and Theoretical Investigation of the Mechanism

Majidian,

Rashid,

Naghdi

et al. 2024

Applied Organom Chemis

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A new asymmetric method for preparing chiral allylic esters from various unactivated alkanes through simultaneous dehydrogenation and enantioselective allylic oxidation in the presence of chiral heterogeneous oxazoline–based ligands is reported for the first time. For this purpose, chiral amino oxazoline ligands, synthesized from chiral amino alcohols and cyanogen bromide, were immobilized on modified MCM‐41 mesoporous silica. These chiral heterogeneous ligands were then characterized using Fourier‐transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and Brunauer–Emmett–Teller and Barrett–Joyner–Halenda techniques. Finally, copper complexes of these ligands were employed in the synthesis of chiral allylic esters, achieving the best result with a 90% yield and 77% enantiomeric excess. Evaluation of the recyclability of the chiral heterogeneous catalysts revealed that they can be reused three times without a noticeable reduction in the results. In addition, the mechanism of formation of the chiral allylic esters was investigated using a density functional theory method.

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Synthesis of new alkenyl iodobenzoate derivatives via Kharasch-Sosnovsky reaction using tert-butyl iodo benzoperoxoate and copper (I) iodide

Cited by 6 publications

References 42 publications

Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch–Sosnovsky reaction

Preparation and DFT studies of chiral Cu (I)-complexes of biphenyl bisoxazolines and their application in enantioselective Kharasch–Sosnovsky reaction

Chiral Pseudohomogeneous Catalyst Based on Amphiphilic Carbon Quantum Dots for the Enantioselective Kharasch–Sosnovsky Reaction

Copper‐Catalyzed Simultaneous Dehydrogenation and Enantioselective Allylic Oxidation of Alkanes Using Chiral Heterogeneous Ligands to Produce Allylic Esters and Theoretical Investigation of the Mechanism

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