The elusive active species in nickel(<scp>ii</scp>)-mediated oxidations of hydrocarbons by peracids: a Ni<sup>II</sup>–oxyl species, an aroyloxy radical, or a Ni<sup>II</sup>–peracid complex?

Zhi-min, WU; Sun, Dongru; Lee, Yong Min; Zhao, Yufen; Nam, Wonwoo; Wang, Yong

doi:10.1039/d3dt01276j

Dalton Trans.

2023

DOI: 10.1039/d3dt01276j

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The elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a Ni^II–oxyl species, an aroyloxy radical, or a Ni^II–peracid complex?

WU Zhi-min

Dongru Sun

Yong Min Lee

et al.

Abstract: Nonheme nickel(II)-mediated oxidations of hydrocarbons by meta-chloroperbenzoic acid (mCPBA) show promising activity and selectivity; however, the active species and the reaction mechanism of these reactions are still elusive after decades...

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Cited by 4 publications

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Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

Bushmin,

Samsonenko,

Talsi

et al. 2023

ChemCatChem

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Nickel(II) complexes with the simple N4 donor aminopyridine ligands BPMEN (N,N′‐dimethyl‐N,N′‐bis(2‐pyridylmethyl)‐1,2‐diaminoethane) and TPA (tris(2‐pyridylmethyl)amine) have been demonstrated to perform as efficient catalysts for the regioselective oxygenation of benzylic C−H groups with m‐chloroperoxybenzoic acid under mild conditions (at 20 °C), typically ensuring >90 % substrate conversions within 1 h at 1 mol % catalyst loadings. Unprecedentedly, replacing the commonly used mixed reaction solvent CH3CN/CH2Cl2 with 2,2,2‐trifluoroethanol diverts the selectivity of the above Ni‐based catalyst systems from hydroxylation/ketonization to trifluoroalkoxylation, with the formation of 1‐phenylalkyl 2,2,2‐trifluoroethyl ethers. The use of 2,2,2‐trifluoroethanol ensures high substrate conversion values (up to 97 %), as well as high selectivity for the ether formation (up to 92 %). Preliminary discussion of the reaction mechanism is given based on the catalytic and literature data.

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Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

Bushmin,

Samsonenko,

Talsi

et al. 2023

ChemCatChem

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C−H Bond Activation Facilitated by Nickel(II) Complexes Having Mighty Claws

Rajeev,

Thomas,

Das

et al. 2024

Eur J Inorg Chem

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Streamline synthesis of cyclic alcohols is an enduring goal in synthetic chemistry. In this regard, a series of aminoquinoline‐based pincer ligands (L1(H) = 2‐(dimethylamino)‐N‐(quinolin‐8‐yl)acetamide, L2(H) = 2‐(diethylamino)‐N‐(quinoline‐8‐yl)acetamide, L3(H) = 2‐(dipropylamino)‐N‐(quinoline‐8‐yl)acetamide and L4(H) = 2‐(dibutylamino)‐N‐(quinolin‐8‐yl)acetamide)) and corresponding nickel(II) complexes of the type [Ni(L)Cl] (1‐4) were synthesized and characterized using modern analytical techniques. Further, the catalytic activity of 1‐4 was investigated for the oxidation of cyclohexane in the presence of different oxidants. All the catalysts showed substantial activity in the presence of m‐CPBA in DCM‐CH3CN (v/v, 3:1) mixture at 60 oC to yield cyclohexanol as the major product and cyclohexanone and caprolactone as the minor products. Under the optimised reaction conditions, catalytic activity was in the order 1 (936) > 2 (892) > 3 (835) > 4 (785), which can be rationalized by the steric‐electronic properties of the respective ligands. Notably, with 1, we could achieve the highest TON (936) reported so far for cyclohexane oxidation using nickel(II) complexes having square planar geometry. The best catalyst, 1 was further used for the oxidation of other cycloalkanes and showed appreciable activity. The formation of chlorinated products in the reaction and product distribution pattern revealed that the oxidation is mediated majorly by 3‐chlorobenzoyloxy radical.

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Recent advances in metal-mediated oxidations with mCPBA

Varala,

Dhadda,

Seema

et al. 2024

Transit Met Chem

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The elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a Ni^II–oxyl species, an aroyloxy radical, or a Ni^II–peracid complex?

Abstract: Nonheme nickel(II)-mediated oxidations of hydrocarbons by meta-chloroperbenzoic acid (mCPBA) show promising activity and selectivity; however, the active species and the reaction mechanism of these reactions are still elusive after decades...

Cited by 4 publications

References 77 publications

Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

C−H Bond Activation Facilitated by Nickel(II) Complexes Having Mighty Claws

Recent advances in metal-mediated oxidations with mCPBA

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The elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a NiII–oxyl species, an aroyloxy radical, or a NiII–peracid complex?

Abstract: Nonheme nickel(II)-mediated oxidations of hydrocarbons by meta-chloroperbenzoic acid (mCPBA) show promising activity and selectivity; however, the active species and the reaction mechanism of these reactions are still elusive after decades...

Cited by 4 publications

References 77 publications

Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

Diverting Ni‐Catalyzed Direct Benzylic C−H Hydroxylation towards Trifluoroethoxylation

C−H Bond Activation Facilitated by Nickel(II) Complexes Having Mighty Claws

Recent advances in metal-mediated oxidations with mCPBA

Contact Info

Product

Resources

About

The elusive active species in nickel(ii)-mediated oxidations of hydrocarbons by peracids: a Ni^II–oxyl species, an aroyloxy radical, or a Ni^II–peracid complex?