66966-42-5Relevant academic research and scientific papers
Hypervalent iodine(III)-Mediated oxidative decarboxylation of β,γ-unsaturated carboxylic acids
Kiyokawa, Kensuke,Yahata, Shunsuke,Kojima, Takumi,Minakata, Satoshi
supporting information, p. 4646 - 4649 (2015/01/09)
A novel oxidative decarboxylation of β,γ-unsaturated carboxylic acids mediated by hypervalent iodine(III) reagents is described. The decarboxylative C-O bond forming reaction proceeded in the presence of PhI(OAc)2 to give the corresponding allylic acetates. In addition, decarboxylative C-N bond formation was achieved by utilizing hypervalent iodine(III) reagents containing an I-N bond. Mechanistic studies suggest the unique reactivity of hypervalent iodine reagents in this ionic oxidative decarboxylation.
Energetic and Rate Effects of the Trifluoromethyl Group at C-2 and C-4 on the Aliphatic Claisen Rearrangement
Gajewski, J. J.,Gee, K. R.,Jurayj, J.
, p. 1813 - 1822 (2007/10/02)
The rate of the Claisen rearrangement is accelerated by a factor of 73 over the parent system when a trifluoromethyl group is present at C-2 of allyl vinyl ether.Ground-state destabilization by the trifluoromethyl group may be responsible for this rate effect.There is little polar character in the transition state, and the transition-state structure has little carbonyl character and only moderate (ca. 1/3) bonding character between the two terminal carbons.The rate enhancement is not observed in the Cope rearrangement of the all-carbon analogue that has a trifluoromet hyl group at C-2.At C-4, the trifluoromethyl group does not bring about a significant rate effect in the Claisen rearrangement relative to the parent system; this result is in contrast to an energetic benefit of 3.5 kcal/mol enjoyed by the system when a cyano group is at C-4, which suggests that radical-stabilizing ability and not electronic-withdrawing ability is important in stabilizing the transition state.
