59671-36-2Relevant articles and documents
Intermolecular C-O Bond Formation with Alkoxyl Radicals: Photoredox-Catalyzed α-Alkoxylation of Carbonyl Compounds
Banoun, Camille,Bourdreux, Flavien,Magnier, Emmanuel,Dagousset, Guillaume
supporting information, p. 8926 - 8930 (2021/11/17)
Due to the high reactivity of alkoxyl (RO·) radicals and their propensity to easily undergo β-scission or Hydrogen Atom Transfer (HAT) reactions, intermolecular alkoxylations involving RO· radicals are barely described. We report herein for the first time the efficient intermolecular trapping of alkoxyl radicals by silyl enol ethers. This photoredox-mediated protocol enables the introduction of both structurally simple and more complex alkoxy groups into a wide range of ketones and amides.
Aliphatic C?C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron–Oxygen Oxidant
Bhattacharya, Shrabanti,Rahaman, Rubina,Chatterjee, Sayanti,Paine, Tapan K.
supporting information, p. 3815 - 3818 (2017/03/27)
A nucleophilic iron–oxygen oxidant, formed in situ in the reaction between an iron(II)–benzilate complex and O2, oxidatively cleaves the aliphatic C?C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C?H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C?C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O2-dependent aliphatic C?C bond cleavage of α-hydroxy ketones containing no α-C?H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1).
Silver ion induced reactions of α-haloimines
De Kimpe, Norbert,Stevens, Christian
, p. 6753 - 6770 (2007/10/02)
The silver ion induced reactions of α-haloimines are markedly different from similar reactions with the corresponding α-haloketones. The various reactions of α-haloimines, including α-alkoxylation 1,2-dehydrohalogenation, rearrangement via α-alkoxyaziridines, Favorskii-rearrangement and Wagner Meerwein rearrangement, are compared and evaluated with silver-induced reactions of α-haloketones The silver ion assisted reactions of α-haloimines are best interpreted in terms of the intermediacy c α-imidoylcarbenium ions or pseudo-α-imidoylcarbenium ions.