scholarly journals Scandium-catalysed intermolecular hydroaminoalkylation of olefins with aliphatic tertiary amines

2016 ◽  
Vol 7 (10) ◽  
pp. 6429-6434 ◽  
Author(s):  
Adi E. Nako ◽  
Juzo Oyamada ◽  
Masayoshi Nishiura ◽  
Zhaomin Hou

A homoleptic scandium trialkyl complex in combination with a borate compound served as an excellent catalyst for the C–H addition of aliphatic tertiary amines to various olefins.

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>


2013 ◽  
Vol 33 (4) ◽  
pp. 717-722 ◽  
Author(s):  
Wei HE ◽  
Songbo HE ◽  
Chenglin SUN ◽  
Kaikai WU ◽  
Liandi WANG ◽  
...  
Keyword(s):  

2012 ◽  
Vol 8 (6) ◽  
pp. 1146-1154
Author(s):  
Rose M. McConnell ◽  
Kalyani Inapudi ◽  
Naveen Kadasala ◽  
Karthika Yarlagadda ◽  
Priya Velusamy ◽  
...  
Keyword(s):  

1987 ◽  
Vol 52 (11) ◽  
pp. 2699-2709 ◽  
Author(s):  
Dalimil Dvořák ◽  
Zdeněk Arnold

Reaction of arylmethylenemalonaldehydes with tributylphosphine and tertiary amines affords compounds of dipolar structure whereas reaction with primary and secondary amines leads to 1,4-addition products. Salts of nucleophilic inorganic anions add to arylmethylenemalonaldehydes under formation of salts of substituted malonaldehydes.


1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.


2013 ◽  
Vol 2013 (32) ◽  
pp. 7286-7290 ◽  
Author(s):  
Aijun Lin ◽  
Hao Peng ◽  
Ablimit Abdukader ◽  
Chengjian Zhu
Keyword(s):  

2020 ◽  
Vol 43 (1) ◽  
pp. 7-14
Author(s):  
Ali Can Ersan ◽  
Azmi Seyhun Kipcak ◽  
Meral Yildirim Ozen ◽  
Nurcan Tugrul

AbstractRecently, sonochemistry has been used for the synthesis of inorganic compounds, such as zinc borates. In this study using zinc sulphate heptahydrate (ZnSO4·7H2O) and boric acid (H3BO3) as starting materials, a zinc borate compound in the form of Zn3B6O12·3.5H2O was synthesized using an ultrasonic probe. Product’s characterization was carried out with using X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR) and Raman spectroscopy. Zinc borate compound’s chemical bond structure was observed with Raman and FTIR. From the XRD results it was seen that Zn3B6O12·3.5H2O can be quickly synthesized upon heating at 80°C and 85°C (55 min) or 90°C (45 min) in very high yield (>90%). The minimum particle size obtained was ~143 μm from the SEM results. Zinc borate compound was synthesized at a lower temperature in less time than other synthesized zinc metal compound in literature.


2021 ◽  
pp. 120443
Author(s):  
Alma Berenice Jasso-Salcedo ◽  
Xia Wang ◽  
Zoltán Bacsik ◽  
Niklas Hedin
Keyword(s):  

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