25097-60-3Relevant academic research and scientific papers
Direct and Regiocontrolled Synthesis of α-Phenyl Ketones from Silyl Enol Ethers and Diphenyliodonium Fluoride
Chen, Kuanchiang,Koser, Gerald F.
, p. 5764 - 5767 (1991)
The efficiacy of diphenyliodonium fluoride (1, DIF) for the phenylation of silyl enol ethers was investigated.When the silyl enol ethers of cyclopentanone, 2-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, acetophenone, 2-pentanone, diisopropyl ketone, and pinacolone were mixed with DIF in tetrahydrofuran, either α-phenyl or α,α-diphenyl ketones were produced and isolated in yields ranging from 20 to 88percent.That the regiochemistry of α-phenylation can be controlled by an appropriate choice of silyl enol ether was demonstrated with the kinetic and thermodynamic silyl enol ethers of 2-methylcyclohexanone, the thermodynamic silyl enol ether of 2-methylcyclopentanone, and the kinetic silyl enol ether of 2-pentanone. 3,3-Dimethyl-2-(silyloxy)-1-butene gave a dehydro dimer of pinacolone with DIF in addition to α-phenylpinacolone, thus suggesting that phenylations of silyl enol ethers with DIF may proceed via radical intermediates.
Photostimulated Nucleophilic Aromatic Substitution for Halides with Carbon Nucleophiles. Preparative and Mechanistic Aspects
Semmelhack, M. F.,Bargar, Thomas
, p. 7765 - 7774 (2007/10/02)
The photo-SRN1 reaction operates efficiently with enolate anions derived from simple ketones and esters, but 2-lithio-1,3-dithiane gives low yields.The sluggish and inefficient reaction of dialkyl-substituted ketone and ester enolates is traced to hydrogen atom transfer from the carbon adjacent to the enolate anion to the transient phenyl radical.The first systematic survey of intramolecular coupling of keton enolate anions shows that six-, seven-, eight-, and ten-membered rings can be formed, although the β-hydrogen transfer becomes important in certain cases.
