83605-32-7Relevant academic research and scientific papers
Contra-Thermodynamic Positional Isomerization of Olefins
Zhao, Kuo,Knowles, Robert R.
supporting information, p. 137 - 144 (2022/01/19)
A light-driven method for the contra-thermodynamic positional isomerization of olefins is described. In this work, stepwise PCET activation of a more substituted and more thermodynamically stable olefin substrate is mediated by an excited-state oxidant an
Installation of a chiral side chain to a 2-alkylidene-1-cycloalkan-1-ol unit by using allylic substitution
Feng, Chao,Kobayashi, Yuichi
, p. 6666 - 6676 (2013/11/06)
The allylic substitution of optically active exocyclic allylic esters of cyclopentane and cyclohexane with ArMgBr-based copper reagents (Ar = aryl) was examined. ArMgBr/Cu(acac)2 in a 2:1 ratio was an adequate reagent to produce the anti-SN2' products efficiently in terms of regioselectivity (95-99a€‰%), chirality transfer (91-99a€‰%), and yield (71-91a€‰%). The Ar groups that were successfully installed include Ph and p-tolyl, those with electron-donating (i.e., p-MeOC6H4) and electron-withdrawing groups (i.e., p-FC6H4), and those with sterically demanding groups (i.e., o-tolyl, o-MeOC6H 4). In an examination of an alkyl reagent, BuMgBr/CuBr·Me 2S in a 2:1 ratio in the presence of ZnI2 afforded the product with high regioselectivity (99a€‰%) and in good yield (91a€‰%). The allylic substitution of exocyclic allylic picolinates (n = 1, 2; R = Ph(CH2)2, iPr, Ph) with a ArCu(acac)MgBr reagent (Ar = Ph, p-tolyl, p-MeOC6H4, p-FC6H4, o-tolyl, o-MeOC6H4) that was derived from a 2:1 ratio of ArMgBr and Cu(acac)2 efficiently afforded the anti-SN2' products in terms of regioselectivity (95-99a€‰%), chirality transfer (91-99a€‰%), and yield (71-91a€‰%). Copyright
Radical ions in photochemistry. 18. The photosensitized (electron transfer) tautomerization of alkenes; the 1,1-diphenyl alkene system
Arnold, Donald R.,Mines, Shelley A.
, p. 2312 - 2314 (2007/10/02)
The photosensitized (electron transfer) irradiation of several conjugated 1,1-diphenyl alkenes, in acetonitrile with 1,4-dicyanobenzene or 1-cyanonaphthalene as electron accepting sensitizer and 2,6-lutidine as base, leads essentially quantitatively to tautomerization to the less stable unconjugated isomer(s).The proposed mechanism for this reaction involves formation of the alkene radical cation and sensitizer radical anion followed by deprotonation of the radical cation, reduction of the resulting radical to the ambident anion by back electron transfer from the radical anion, and reprotonation.There are several steps in this mechanism that could control the ratio of isomers.Evidence is provided that, at least in some cases, it is the relative rate of deprotonation from the isomeric radical cations that is the determining factor.This rate is influenced by the conformation of the radical cation; the carbon-hydrogen bond involved in the deprotonation step must overlap with the singly occupied molecular orbital.
