NHC-Copper-Catalyzed Tandem Hydrocupration and Allylation of Alkenyl Boronates

Synthesis ◽  
2017 ◽  
Vol 49 (21) ◽  
pp. 4753-4758 ◽  
Author(s):  
Jaesook Yun ◽  
Won Jang ◽  
Jung Han

A tandem hydrocupration/allylation of alkenyl boronates efficiently proceeds with NHC-copper catalysts using hydrosilane and allyl phosphate as reagents. In the presence of IMes–Cu catalyst, the allylation of in situ generated Β-α-copper intermediates smoothly occurs to give homoallylic boronates in high yields, despite competitive side reaction pathways. Mono- and disubstituted alkenyl boronates were effective in the reaction with terminal allyl phosphates, but trisubstituted substrates showed limited reactivity.

2019 ◽  
Vol 23 (8) ◽  
pp. 860-900 ◽  
Author(s):  
Chander P. Kaushik ◽  
Jyoti Sangwan ◽  
Raj Luxmi ◽  
Krishan Kumar ◽  
Ashima Pahwa

N-Heterocyclic compounds like 1,2,3-triazoles serve as a key scaffolds among organic compounds having diverse applications in the field of drug discovery, bioconjugation, material science, liquid crystals, pharmaceutical chemistry and solid phase organic synthesis. Various drugs containing 1,2,3-triazole ring which are commonly available in market includes Rufinamide, Cefatrizine, Tazobactam etc., Stability to acidic/basic hydrolysis along with significant dipole moment support triazole moiety for appreciable participation in hydrogen bonding and dipole-dipole interactions with biological targets. Huisgen 1,3-dipolar azide-alkyne cycloaddition culminate into a mixture of 1,4 and 1,5- disubstituted 1,2,3-triazoles. In 2001, Sharpless and Meldal came across with a copper(I) catalyzed regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles by cycloaddition between azides and terminal alkynes. This azide-alkyne cycloaddition has been labelled as a one of the important key click reaction. Click synthesis describes chemical reactions that are simple to perform, gives high selectivity, wide in scope, fast reaction rate and high yields. Click reactions are not single specific reaction, but serve as a pathway for construction of simple to complex molecules from a variety of starting materials. In the last few decades, 1,2,3-triazoles attracted attention of researchers all over the world because of their broad spectrum of biological activities. Keeping in view the biological importance of 1,2,3-triazole, in this review we focus on the various synthetic routes for the syntheisis of 1,4-disubstituted 1,2,3-triazoles. This review involves various synthetic protocols which involves copper and non-copper catalysts, different solvents as well as substrates. It will boost synthetic chemists to explore new pathway for the development of newer biologically active 1,2,3-triazoles.


2016 ◽  
Vol 40 (12) ◽  
pp. 10300-10304 ◽  
Author(s):  
Raktani Bikshapathi ◽  
Parvathaneni Sai Prathima ◽  
Vaidya Jayathirtha Rao

An efficient, eco-friendly protocol for selective oxidation of primary and secondary Baylis–Hillman alcohols to the corresponding carbonyl compounds in high yields has been developed with 2-iodosobenzoic acid (IBA).


2018 ◽  
Vol 30 (1) ◽  
pp. 77-84 ◽  
Author(s):  
Min-Yu Lin ◽  
Yen-Hua Chen ◽  
Jey-Jau Lee ◽  
Hwo-Shuenn Sheu

2021 ◽  
Vol 3 ◽  
Author(s):  
Wenjia Wang ◽  
Xiaoxing Wang ◽  
Guanghui Zhang ◽  
Ke Wang ◽  
Fu Zhang ◽  
...  

Previously, we reported a strong Fe-Cu synergy in CO2 hydrogenation to olefin-rich C2+ hydrocarbons over the γ-Al2O3 supported bimetallic Fe-Cu catalysts. In this work, we aimed to clarify such a synergy by investigating the catalyst structure, Fe-Cu interaction, and catalyst surface properties through a series of characterizations. H2-TPR results showed that the addition of Cu made both Fe and Cu easier to reduce via the strong interaction between Fe and Cu. It was further confirmed by X-ray absorption spectroscopy (XAS) and TEM, which showed the presence of metallic Fe and Fe-Cu alloy phases in the reduced Fe-Cu(0.17) catalyst induced by Cu addition. By correlating TPD results with the reaction performance, we found that the addition of Cu enhanced both the moderately and strongly adsorbed H2 and CO2 species, consequently enhanced CO2 conversion and C2+ selectivity. Adding K increased the adsorbed-CO2/adsorbed-H2 ratio by greatly enhancing the moderately and strongly adsorbed CO2 and slightly suppressing the moderately and strongly adsorbed H2, resulting in a significantly increased O/P ratio in the produced hydrocarbons. The product distribution analysis and in situ DRIFTS suggested that CO2 hydrogenation over the Fe-Cu catalyst involved both an indirect route with CO as the primary product and a direct route to higher hydrocarbons.


2007 ◽  
Vol 72 (8) ◽  
pp. 1094-1106 ◽  
Author(s):  
Szilárd Csihony ◽  
László T. Mika ◽  
Gábor Vlád ◽  
Katalin Barta ◽  
Christian P. Mehnert ◽  
...  

A chlorine-free catalyst, prepared in situ from Cu(II) acetate and 2,2'-bipyrimidine, can be used for the oxidative carbonylation of methanol to dimethyl carbonate. In situ high pressure IR and NMR spectroscopic studies suggest the formation of [Cu(2,2'-bipyrimidine)(CO)- (OMe)] as one of the key intermediates. The catalytic performance of the 2,2'-bipyrimidine-modified Cu-catalyst is similar to the CuCl-based system. The chlorine free catalyst can be immobilized by using the copolymer of 5-vinyl-2,2'-bipyrimidine and styrene.


Synlett ◽  
2018 ◽  
Vol 29 (15) ◽  
pp. 2015-2018 ◽  
Author(s):  
William Wulff ◽  
Xin Zhang ◽  
Yijing Dai

An efficient method was developed for the synthesis of α-amino ketones from α-hydroxy imines. The reaction occurs through an α-iminol rearrangement involving the migration of a substituent of the carbinol carbon to the imine carbon. The optimal catalysts were found to be silica gel or montmorillonite K 10, which effected migration of a variety of aryl and alkyl substituents in high yields. The rearrangement can also be carried out on imines generated in situ from aldehydes and amines in essentially the same yields as those from the preformed imines.


2012 ◽  
Vol 170-173 ◽  
pp. 1187-1191
Author(s):  
Ya Hui Jia ◽  
Xiao Ping Xie ◽  
Ai Li Lu

Colabed methane system is a natural system that consists of coal seams, coalbed methane in them and surrounding rocks. As an unconventional natural gas, reservoir and conservation of coalbed methane are different from those of conventional hydrocarbon. The Qinshui Basin, covering an area about 30,000sq.km in southeastern Shanxi Province, has abundant coalbed methane resources in the carboniferous Taiyuan formation and permian Shanxi formation, with an in-situ methane resource 3.3×1012 m3.In this study, the structural deformation and tectonic evolution of coalbed methane system in Qinshui basin were reported. Relationships between structural deformation and the formation of coalbed methane reservoir in Qinshui Basin were also discussed. The results show that Yangquan-Shouyang area in the north part of the basin and Tunliu-Xiangyuan area in the east are favorable for formation coalbed methane system. In contrast, Jincheng-Qinshui area in the south part of basin and the Qinyuan area in the middle of basin are favorable for both the formation of coalbed methane reservoirs and high yields as well.


Synlett ◽  
2017 ◽  
Vol 28 (20) ◽  
pp. 2817-2822 ◽  
Author(s):  
Marthe Ketels ◽  
Dorothée Ziegler ◽  
Paul Knochel

A mild and general metalation procedure for the functionalization of 1,2-dicyanobenzene and related polyfunctionalized benzonitriles using a commercially available continuous flow setup is reported. The addition of TMPLi (TMP = 2,2,6,6-tetramethylpiperidyl) to a mixture of an aromatic substrate with a metallic salt such as ZnCl2 under appropriate conditions (0 °C, 20 s) leads to fast in situ lithiation of the arene followed by transmetalation with ZnCl2 to afford the corresponding functionalized arylzinc compound that were trapped with various electrophiles in high yields. The reaction scope of these in situ trapping metalations in flow is broader and needs less equivalents of the base and the metal salt than the corresponding batch procedure.


2019 ◽  
Vol 25 (1) ◽  
pp. 85-90 ◽  
Author(s):  
M. Javad Poursharifi ◽  
Mohammad M. Mojtahedi ◽  
M. Saeed Abaee ◽  
Mohammad M. Hashemi

AbstractA method is developed for in situ generation of 1,3-dioxan-5-one derivatives 2. These compounds are simple precursors for accessing carbohydrate structures and previously had to be produced via stepwise procedures using excessive amounts of reagents. In the present work, three different derivatives of 2 were synthesized via the reaction of trialkoxyalkanes with dihydroxyacetone dimer 1 in the presence of acetic acid as the catalyst. In the same pot, derivatives of 2 were reacted with aromatic aldehydes and 30 mol% of pyrrolidine to obtain high yields of the respective bischalcones 3 within short time periods.


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