Phenalenyl in a Different Role: Catalytic Activation through the Nonbonding Molecular Orbital
作者:Sudipta Raha Roy、A. Nijamudheen、Anand Pariyar、Anup Ghosh、Pavan K. Vardhanapu、Prasun K. Mandal、Ayan Datta、Swadhin K. Mandal
DOI:10.1021/cs5010695
日期:2014.12.5
We have demonstrated that the nonbonding molecular orbital (NBMO) of the phenalenyl (PLY) cation can be used as a Lewis acid catalyst for different organic transformations. Detailed computational and spectroscopic studies for the aminolysis reaction of epoxide reveal that this catalysis works through a different mechanism, and the phenalenyl cation activates the amine moiety using its empty NBMO, which triggers the epoxide ring-opening reaction. It has been shown that the energy of the NBMO of PLY cation plays a key role in modulating the catalytic activity. This study establishes that the cationic state of phenalenyl unit is useful not only for construction of the spin memory device by external spin injection using its NBMO, but in addition, the same NBMO can act as an organic Lewis acceptor unit to influence the catalytic outcome of a homogeneous reaction.
Aluminium triflate: an efficient recyclable Lewis acid catalyst for the aminolysis of epoxides
作者:D. Bradley G. Williams、Michelle Lawton
DOI:10.1016/j.tetlet.2006.07.036
日期:2006.9
Epoxides are powerful starting materials for a range of useful materials and can be converted into, amongst others, amino alcohols. In this work, a range of epoxides was ring-opened using various alkyl- and arylamines under the action of aluminium triflate as a catalyst. This catalyst was found to be highly active, producing the desired amino alcohol products in high yields with low catalyst loadings. Additionally, it was shown that the aluminium triflate catalyst is recyclable by simple extraction into water and may be re-used several times. (c) 2006 Elsevier Ltd. All rights reserved.