Hydrogen Peroxide Bleaching of Amaranth Catalysed by Nickel(II) Nitrilotriacetic Acid

Paradis, Paul M.

doi:10.1177/174751989902300522

Cited by 1 publication

(1 citation statement)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Until recently, nickel/peroxide systems have been only used in a few oxygen transfer processes. − In 2016, the Chatani group reported dicumyl peroxide as a methyl source for the Ni-catalyzed aryl C(sp 2 )–H methylation (Scheme B) . Later, several Ni-catalyzed alkylations of C(sp 2 )–H and N–H bonds with organic peroxides as the alkyl source were discovered (Scheme B). − However, there is only one known example of Ni-catalysts that allows methylation at C(sp 3 )–H groups with dialkyl peroxides but with the additional assistance of Ir photoredox catalysis (Scheme C) …”

Section: Introductionmentioning

confidence: 99%

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

et al. 2023

View full text Add to dashboard Cite

The reaction of Ni(II) acetate with diacyl peroxides produces high-valence Ni-species capable of catalytic oxidative acyloxylation of C(sp3)–H bonds in ethers, ketones, and alkanes. The desired esters were obtained in 20–82% yields. Computational analysis suggests that activation of the peroxide moiety produces a dynamically interconverting mixture of catalytic Ni-species in the formal Ni(III) state. Remarkably, in these species, coordination of the RCO2 group at Ni preserves radical character at the carboxylate moiety (i.e., carboxylate radical acts as an “L-ligand”), so the latter can induce fast C–H abstraction. The spirocyclopropyl moiety prevents premature radical decarboxylation via a combination of hybridization factors and stereoelectronic effects. A variety of viable C–H activation patterns were identified experimentally and computationally.

show abstract

Section: Introductionmentioning

confidence: 99%

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

et al. 2023

View full text Add to dashboard Cite

show abstract

Hydrogen Peroxide Bleaching of Amaranth Catalysed by Nickel(II) Nitrilotriacetic Acid

Abstract: The complex of NiII with nitrilotriacetic acid (NTA) (but not other aminocarboxylate complexes) autocatalyses the hydrogen peroxide bleaching of amaranth, although the reaction is inhibited by the absence of light or presence of alcohol, suggesting a radical-based mechanism.

Cited by 1 publication

References 11 publications

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Contact Info

Product

Resources

About

Hydrogen Peroxide Bleaching of Amaranth Catalysed by Nickel(II) Nitrilotriacetic Acid

Abstract: The complex of NiII with nitrilotriacetic acid (NTA) (but not other aminocarboxylate complexes) autocatalyses the hydrogen peroxide bleaching of amaranth, although the reaction is inhibited by the absence of light or presence of alcohol, suggesting a radical-based mechanism.

Cited by 1 publication

References 11 publications

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Contact Info

Product

Resources

About

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides