1608461-37-5Relevant academic research and scientific papers
Intermolecular Aminoallylation of Alkenes Using Allyl-Oxyphthalimide Derivatives: A Case Study in Radical Polarity Effects
Lardy, Samuel W.,Schmidt, Valerie A.
, p. 6796 - 6799 (2019/11/03)
A case study on the polarity effects of radical mediated intermolecular alkene aminoallylation is presented herein. This radical group transfer method pairs vinyl ethers with electronically deficient allyl-oxyphthalimide derivatives to give difunctionalized products while illustrating the guiding effects of polarity on this radical reactivity.
Effect of Lewis acids and low temperature initiators on the allyl transfer reaction involving phthalimido-N-oxyl radical
Patil, Shradha,Chen, Liang,Tanko, James M.
supporting information, p. 7029 - 7033 (2015/01/09)
Previously, we reported allyl transfer reactions of allyl bromide and allyl phthalimido-N-oxyl substrates with hydrocarbons that result in CC bond formation. In both cases, efficient chain transfer processes along with high reaction yields were observed. Since PINO chemistry leads to an environmentally friendly method of hydrocarbon functionalization, additional studies were performed in order to improve the process. To expand the utility of this reaction, we carried out experiments to optimize reaction conditions and tested the effect of Lewis acids and low temperature initiators. Although allyl-PINO substrates reacted slightly slower than the bromides, the reactions were cleaner with little or no side products. The chain lengths for these reactions were compromised at lower temperatures, attributable to the high activation energy required for the hydrogen atom abstraction by PINO. The addition of a Lewis acid catalyst (AlCl3) improves the product yield and reaction rate, possibly due to the formation of a PINO/AlCl3 complex which lowers the activation energy for hydrogen abstraction step.
C-H Bond Functionalization with the Formation of a C-C Bond: A Free Radical Condensation Reaction Based on the Phthalimido-N-oxyl Radical
Patil, Shradha,Chen, Liang,Tanko, James M.
supporting information, p. 502 - 505 (2015/10/05)
The development of a new chemical process that effects the conversion RH + C=C-C-X → R-C-C=C + HX, in which X is the phthalimido-N-oxyl radical (PINO·), is reported. The reaction yields are high, mass balances are excellent, and C-H bond functionalization and C-C bond formation are achieved in a single transformation. The byproduct of the reaction, N-hydroxyphthalimide, precipitates from solution and can be easily removed by simple filtration (and recycled). The kinetic chain lengths are shorter and the reaction times are longer (relative to those of the analogous reactions of allyl bromides), most likely because PINO· is a less-reactive hydrogen-atom abstractor. There appears to be no significant difference in efficiency in the addition-elimination steps. Competition experiments reveal that Br· and PINO· are comparable in leaving group ability.
