Methods of Transition Metal-Catalyzed Asymmetric Oxidation

Yao, Biao; Wu, Jiahao; Wang, Yu; Jiang, Huanfeng

doi:10.6023/cjoc202005095

Cited by 6 publications

(3 citation statements)

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“…[11] Moreover, the high stability of nitrogen ligands is widely used in palladium-catalyzed reactions. [12] Herein, we explored the influencing factors during the palladium-catalyzed asymmetric cyclization of 3-phenylpropynoic acid and styrene using NCP and chiral pyridine oxazoline (PyOX) ligands and the generalizability of the reaction under this condition.…”

Section: Introductionmentioning

confidence: 99%

“…N ‐Chlorophthalimide (NCP), a bifunctional reagent with oxidizing and chlorine source, can well solve the problem of chlorine ions interfering with the reaction and is widely used in palladium‐catalyzed chlorination reaction [11] . Moreover, the high stability of nitrogen ligands is widely used in palladium‐catalyzed reactions [12] . Herein, we explored the influencing factors during the palladium‐catalyzed asymmetric cyclization of 3‐phenylpropynoic acid and styrene using NCP and chiral pyridine oxazoline (PyOX) ligands and the generalizability of the reaction under this condition.…”

Section: Introductionmentioning

confidence: 99%

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Factors Influencing the Palladium‐Catalyzed Asymmetric Synthesis of α‐Chloromethylene‐γ‐butyrolactones

Yao,

Xiong,

Jin

et al. 2024

Eur J Org Chem

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Abstractα‐Methylene‐γ‐butyrolactone is an important skeleton in many natural products and pharmaceuticals. The factors influencing the palladium‐catalyzed asymmetric synthesis of α‐chloromethylene‐γ‐butyrolactones were investigated, including ligands, additives, the chlorine source, temperature, and solvents. We found that the reaction had broad substrate scope for the synthesis of the corresponding chiral products when the ligand, chlorine source and additives were optimized. The results will improve the catalytic synthesis of chiral α‐chloromethylene‐γ‐butyrolactones.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Factors Influencing the Palladium‐Catalyzed Asymmetric Synthesis of α‐Chloromethylene‐γ‐butyrolactones

Yao,

Xiong,

Jin

et al. 2024

Eur J Org Chem

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“…Among these methods, the catalysts based on the late 3d-transition metals, which are inspired by the oxidation reactions featured in enzymatic processes, have drawn much attention (Figure a). Chiral Mn–O and Fe–O catalysts have been established as biomimetic oxidation systems, allowing asymmetric epoxidation and other oxidation reactions. − The Salen-Mn catalytic epoxidation of alkene, also known as Jacobsen–Katsuki epoxidation, represents a significant breakthrough. , The Mn and Fe catalysts of chiral hybrid nitrogen-based ligand series have also been disclosed as chiral heme and nonheme enzyme mimics for asymmetric epoxidation by several research groups. ,,− However, the neighboring cobalt complexes for epoxidation via the generation of high-valent Co–O complexes would seem to be reactive but difficult to achieve due to ligand field arguments called as “oxo-wall.” − In brief, the late-transition metal d orbitals filled with more valence electrons repulse the oxo ligands obviously; thus, the Co–O unit becomes much more unstable and reactive. Therefore, the asymmetric version of epoxidation involving Co–O complexes has not been accomplished, although Kochi and co-workers have postulated an active cobalt(IV)-oxo species in epoxidation with iodosylbenzene using the tetradentate amide ligands early in 1987 .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Epoxidation of Alkenes Catalyzed by a Cobalt Complex

Jiang

et al. 2023

J. Am. Chem. Soc.

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Asymmetric epoxidation of alkenes catalyzed by nonheme chiral Mn−O and Fe−O catalysts has been well established, but chiral Co−O catalysts for the purpose remain virtually undeveloped due to the oxo wall. Herein is first reported a chiral cobalt complex to realize the enantioselective epoxidation of cyclic and acyclic trisubstituted alkenes by using PhIO as the oxidant in acetone, wherein the tetraoxygen-based chiral N,N′-dioxide with sterically hindered amide subunits plays a crucial role in supporting the formation of the Co−O intermediate and enantioselective electrophilic oxygen transfer. Mechanistic studies, including HRMS measurements, UV−vis absorption spectroscopy, magnetic susceptibility, as well as DFT calculations, were carried out, confirming the formation of Co−O species as a quartet Co(III)-oxyl tautomer. The mechanism and the origin of enantioselectivity were also elucidated based on control experiments, nonlinear effects, kinetic studies, and DFT calculations.

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Palladium Catalyzed Aerobic Oxidative Amination of Alkenes

Meng

Liu

et al. 2023

Asian J Org Chem

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Amines are widely applied in the chemical and pharmaceutical industries, and the development of synthetic methods for their preparation is driven by their importance. The amination of alkenes is a direct and efficient method for the construction of amines, of which oxidative amination is more valuable because it can give the desired products with greater functionality and flexibility. In oxidative amination, using molecular oxygen (O2) as a terminal oxidant has promising industrial application prospects. In recent years, the palladium‐catalyzed aerobic oxidation of alkenes has seen significant progress, and its related research has also been extended to the aerobic oxidative amination of alkenes. The corresponding oxidation systems have been developed from early research involving the introduction of cocatalysts to the more recent systems which utilize auxiliary ligands instead of cocatalysts. In this review, the advancements in the palladium‐catalyzed aerobic oxidative amination of monoalkenes and conjugated dienes over the last two decades are discussed, with emphasis on aerobic oxidation process and their associated mechanisms.

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Methods of Transition Metal-Catalyzed Asymmetric Oxidation

Cited by 6 publications

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Factors Influencing the Palladium‐Catalyzed Asymmetric Synthesis of α‐Chloromethylene‐γ‐butyrolactones

Factors Influencing the Palladium‐Catalyzed Asymmetric Synthesis of α‐Chloromethylene‐γ‐butyrolactones

Asymmetric Epoxidation of Alkenes Catalyzed by a Cobalt Complex

Palladium Catalyzed Aerobic Oxidative Amination of Alkenes

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