90645-55-9Relevant articles and documents
A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols
Gu, Xin,Wendlandt, Alison E.,Zhang, Yu-An
supporting information, p. 599 - 605 (2022/01/03)
Here, we report the selective, catalytic isomerization of cis-1,2-diols to trans-diequatorial-1,2-diols. The method employs triphenylsilanethiol (Ph3SiSH) as a catalyst and proceeds under mild conditions in the presence of a photoredox catalyst and under
Trapping of the 6,6-Dimethylbicyclohept-2-yl Free Radical by SH2 Reaction upon Peracid
Fossey, Jacques,Lefort, Daniel,Sorba, Janine
, p. 3584 - 3587 (2007/10/02)
The free radical 6,6-dimethylbicyclohept-2-yl (7) has been obtained by decarboxylation of cis- or trans-6,6-dimethylbicycloheptane-2-peroxycarboxylic acids (6a and 6b). 7 trapped by reaction with the initial peracid gave a stereochemical mixture of α- and β-nopinol (8a and 8b).The ratio 8b/8a is around 12, independent of the initial peracid 6a or 6b and its initial concentrations.This value is mainly due to the steric effect of one of the methyl groups branched on C7 in 7.The structure of 7 is discussed.By a competitive reaction 7 undergoes ring opening to afford 2-(3-cyclohexenyl)-2-propyl free radical (9) which by reaction upon peracid leads to 2-(3-cyclohexenyl)-2-propanol (10). 7 was successfully trapped because its reaction with peracid is rapid enough.The ratio of the two alcohols 8/10 leads to an estimation of 1*106 M-1 s-1 for the rate constant of the reaction of 7 with peracids
