81090-01-9Relevant academic research and scientific papers
Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
supporting information, p. 3421 - 3426 (2020/06/25)
It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
Copper(II)-acid co-catalyzed intermolecular substitution of electron-rich aromatics with diazoesters
Tayama, Eiji,Ishikawa, Moe,Iwamoto, Hajime,Hasegawa, Eietsu
, p. 5159 - 5161 (2012/10/07)
The intermolecular aromatic substitution of N,N-dialkylanilines and alkoxybenzenes with diazoesters is shown to proceed in the presence of catalytic amounts of both copper(II) salt and acid (Lewis or Br?nsted). This method is a mild and rare metal-free C-C bond formation reaction between aromatic (sp2) and aliphatic (sp3) carbons.
Copper(II) triflate catalyzed intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters
Tayama, Eiji,Yanaki, Tomoyo,Iwamoto, Hajime,Hasegawa, Eietsu
supporting information; experimental part, p. 6719 - 6721 (2011/02/28)
The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is achieved under mild conditions in the presence of a catalytic amount of copper(II) triflate (up to 89 % yield). The scope and limitations regarding substrates, diazo esters, and ligands in this reaction are described. The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is shown to proceed under mild conditions in the presence of a catalytic amount of copper(II) triflate/ligand complex(up to 89 % yield). The scope and limitations regarding substrates, diazoesters, and ligands in this reaction are described. Copyright
New rhodium complexes with P,N-ligands possessing a hydroxy or methoxy group. Synthesis, characterization and application to hydroformylation of styrene
Kostas, Ioannis D.,Screttas, Constantinos G.
, p. 1 - 6 (2007/10/03)
Two new cationic rhodium(I) complexes containing a phosphino amino alcohol ligand and a methoxy amino phosphine, respectively, have been prepared. According to IR and NMR data the ligands are P,N-bonded and coordination of the hydroxy or the methoxy group to the metal does not take place. The complexes were applied to the hydroformylation of styrene and displayed a quantitative chemoselectivity for aldehydes with a very good branched:linear ratio. The reaction rate is higher using the complex possessing the methoxy group as opposed to the hydroxy group.
