80089-25-4Relevant academic research and scientific papers
N2 extrusion and co insertion: A novel palladium-catalyzed carbonylative transformation of aryltriazenes
Li, Wanfang,Wu, Xiao-Feng
, p. 1910 - 1913 (2015/04/27)
A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H. Nitrogen was released from the substrates and CO formally inserted. Aryl bromides, iodides, alkynes, and free hydroxyl groups can be tolerated in this transformation.
Reevaluation of the 2-nitrobenzyl protecting group for nitrogen containing compounds: An application of flow photochemistry
Wendell, Chloe I.,Boyd, Michael J.
supporting information, p. 897 - 899 (2015/02/05)
Photochemistry under continuous flow conditions has many potential benefits for photochemical reactions that are problematic in batch. The 2-nitrobenzyl moiety is a photolabile protecting group for nitrogen. However, N-deprotection is generally impractical and, therefore, has not been extensively adopted. This Letter reports significant improvements in the N-deprotection of the 2-nitrobenzyl group through the application of continuous flow photolysis. This procedure was applied to a variety of substrates including indoles, indazoles, pyrazoles and secondary amines. Significant improvement in yield, reaction time and scalability was observed under continuous flow conditions.
Gas-phase fragmentation of the protonated benzyl ester of proline: Intramolecular electrophilic substitution versus hydride transfer
Li, Fei,Zhang, Xiaoping,Zhang, Huarong,Jiang, Kezhi
, p. 423 - 429 (2013/06/04)
In this study, the gas phase chemistry of the protonated benzyl esters of proline has been investigated by electrospray ionization mass spectrometry and theoretical calculation. Upon collisional activation, the protonated molecules undergo fragmentation reactions via three primary channels: (1) direct decomposition to the benzyl cation (m/z 91), (2) formation of an ion-neutral complex of [benzyl cation + proline]+, followed by a hydride transfer to generate the protonated 4,5-dihydro-3H-pyrrole-2-carboxylic acid (m/z 114), and (3) electrophilic attack at the amino by the transferring benzyl cation, and the subsequent migration of the activated amino proton leading to the simultaneous loss of (H2O + CO). Interestingly, no hydrogen/deuterium exchange for the fragment ion m/z 114 occurs in the d-labeling experiments, indicating that the transferring hydride in path-b comes from the methenyl hydrogen rather than the amino hydrogen. For para-substituted benzyl esters, the presence of electron-donating substituents significantly promotes the direct decomposition (path-a), whereas the presence of electron-withdrawing ones distinctively inhibits that channel. For the competing channels of path-b and path-c, the presence of electron-donating substituents favors path-b rather than path-c, whereas the presence of electron-withdrawing ones favors path-c rather than path-b. Copyright 2013 John Wiley & Sons, Ltd. Copyright
