62586-99-6Relevant academic research and scientific papers
MgCl2-accelerated addition of functionalized organozinc reagents to aldehydes, ketones, and carbon dioxide
Metzger, Albrecht,Bernhardt, Sebastian,Manolikakes, Georg,Knochel, Paul
supporting information; experimental part, p. 4665 - 4668 (2010/08/19)
Figure Presented Pump it up! The sluggish reactivity of organozinc reagents in additions to aldehydes, ketones, and CO2 can be increased by MgCl2, which is usually generated in the preparation of the zinc reagent. The direct reaction with CO2, in particular, opens an expeditious route to phenylacetic acid derivatives, as demonstrated in a short synthesis of ibuprofen (see scheme).
Oxygen acidity of ring methoxylated 1,1-diarylalkanol radical cations bearing α-cyclopropyl groups. The competition between O-neophyl shift and C-cyclopropyl β-scission in the intermediate 1,1-diarylalkoxyl radicals
Bietti, Massimo,Fiorentini, Simone,Pato, Iria Perez,Salamone, Michela
, p. 3167 - 3175 (2007/10/03)
A product and time-resolved kinetic study on the reactivity of the radical cations generated from cyclopropyl(4-methoxyphenyl)phenylmethanol (1) and cyclopropyl[bis(4-methoxyphenyl)]methanol (2) has been carried out in aqueous solution. In acidic solution, 1.+ and 2.+ display very low reactivities toward fragmentation, consistent with the presence of groups at Cα (aryl and cyclopropyl) that after Cα-C β bond cleavage would produce relatively unstable carbon-centered radicals. In basic solution, 1.+ and 2.+ display oxygen acidity, undergoing -OH-induced deprotonation from the α-OH group, leading to the corresponding 1,1-diarylalkoxyl radicals 1r. and 2r., respectively, as directly observed by time-resolved spectroscopy. The product distributions observed in the reactions of 1.+ and 2.+ under these conditions (cyclopropyl phenyl ketone, cyclopropyl(4-methoxyphenyl) ketone, and 4-methoxybenzophenone from 1.+; cyclopropyl(4-methoxyphenyl) ketone and 4,4′- dimethoxybenzophenone from 2.+) have been rationalized in terms of a water-induced competition between O-neophyl shift and C-cyclopropyl β-scission in the intermediate 1,1-diarylalkoxyl radicals 1r. and 2r..
