Microbial cyclosophoraose as a catalyst for the synthesis of diversified indolyl 4H-chromenes via one-pot three component reactions in water

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Microbial cyclosophoraose as a catalyst for the synthesis of diversified indolyl 4H-chromenes via one-pot three component reactions in water

Green Chem., 2016, Advance Article DOI: 10.1039/C6GC00137H, Paper Someshwar D. Dindulkar, Daham Jeong, Eunae Cho, Dongjin Kim, Seunho Jung A novel biosourced saccharide catalyst, microbial cyclosophoraose, a cyclic [small beta]-(1,2) glucan, was used for the synthesis of indolyl 4H-chromenes via a one pot three-component Knoevenagel-Michael addition-cyclization reaction in water under neutral conditions.

Someshwar D. Dindulkar,^a   Daham Jeong,^a   Eunae Cho,^a  Dongjin Kim^b and   Seunho Jung*^ac  

*Corresponding authors

^aInstitute for Ubiquitous Information Technology and Applications (UBITA) & Center for Biotechnology Research in UBITA (CBRU), Konkuk University, Seoul 143-701, South Korea
E-mail: shjung@konkuk.ac.kr

^bNelson Mandela African Institution of Science and Technology, PO box 447, Arusha, Tanzania

^cDepartment of Bioscience and Biotechnology, Microbial Carbohydrate Resource Bank (MCRB), Konkuk University, Seoul 143-701, South Korea

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00137H

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00137H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

As a novel biosourced saccharide catalyst, microbial cyclosophoraose, a cyclic β-(1,2) glucan, was used for the synthesis of therapeutically important versatile indolyl 4H-chromenes via a one pot three-component Knoevenagel–Michael addition–cyclization reaction of salicylaldehyde, 1,3-cyclohexanedione/dimedone, and indoles in water under neutral conditions. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, green chemistry metric calculations were carried out for a model reaction, indicating the satisfactory greener approach of this method, with a low E-factor (0.18) and high atom economy (AE = 91.20%). The key features of this protocol are based on two critical factors where the first is to use a novel eco-friendly supramolecular carbohydrate catalyst and the second is its fine green properties such as compatibility with various substituted reactants, recyclability of the catalyst, chromatography-free purification, high product selectivity, and clean conversion with moderate to excellent yields in an aqueous medium.

 

 

 

////////Microbial cyclosophoraose,  catalyst,  synthesis,  diversified indolyl 4H-chromenes, one-pot three component reactions, water

“On water” reactivity between carbohydrate-derived nitroalkenes and furans

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00555A, Paper

Veronica Luque-Agudo, Maria Victoria Gil, Emilio Roman, Jose Antonio Serrano
Eco-friendly “on water” reactions of carbohydrate-derived nitroalkenes with furan, 2-methylfuran and furfuralN,N-dimethylhydrazone have been investigated under different mixing methods, such as a magnetic stirrer and a wrist-action shaker.

“On water” reactivity between carbohydrate-derived nitroalkenes and furans

Verónica Luque-Agudo,^a   María Victoria Gil,*^a  Emilio Román^a and   José Antonio Serrano^a  

*Corresponding authors

^aIACYS-Unidad de Química Verde y Desarrollo Sostenible, Departamento de Química Orgánica e Inorgánica, Facultad de Ciencias, Universidad de Extremadura, Badajoz, España
E-mail: vgil@unex.es
Fax: +34 924 271 149

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00555A

http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00555A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Eco-friendly “on water” reactions of carbohydrate-derived nitroalkenes with furan, 2-methylfuran and furfural N,N-dimethylhydrazone have been investigated under different mixing methods, such as a magnetic stirrer and a wrist-action shaker. Cyclic and acyclic furyl derivatives from carbohydrates were obtained with high diastereoselectivity.

///////”On water”,  reactivity,  carbohydrate-derived nitroalkenes,  furans

Selective aerobic oxidation of furfural to maleic anhydride with heterogeneous Mo-V-O catalysts

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00508J, Communication

Xiukai Li, Ben Ho, Yugen Zhang
A binary Mo-V metal oxide catalyzed the selective aerobic oxidation of furfural to maleic anhydride (MA) with up to 65% yield.

Selective aerobic oxidation of furfural to maleic anhydride with heterogeneous Mo-V-O catalysts

Xiukai Li,^a   Ben Ho^a and   Yugen Zhang*^a  

*Corresponding authors

^aInstitute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos, Singapore
E-mail: ygzhang@ibn.a-star.edu.sg

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00508J, http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00508J?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

A heterogeneous catalytic system using binary Mo–V metal oxides as catalysts was demonstrated for the selective aerobic oxidation of furfural to maleic anhydride (MA). Aspects such as the solvent for the reaction, the phase composition and the Mo/V ratio for the catalyst, and other reaction conditions were investigated in detail. Up to 65% yield of MA was achieved over the Mo₄VO₁₄ catalyst in an acetic acid solvent under optimal conditions. The catalyst could be recycled. The reaction mechanism and the role of the acetic acid solvent were also discussed.

 

 

//////Selective aerobic oxidation, furfural, maleic anhydride,  heterogeneous Mo-V-O catalysts

Cooperative catalyst system for the synthesis of oleochemical cyclic carbonates from CO2 and renewables

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC00671J, Paper

Nils Tenhumberg, Hendrik Buttner, Benjamin Schaffner, Daniela Kruse, Michael Blumenstein, Thomas Werner
Taking Control! The binary catalyst system composed of MoO₃ and an organic phoshponium salt [Bu₄P]X proved very efficient to produce oleochemical cyclic carbonates from renewables.

Cooperative catalyst system for the synthesis of oleochemical cyclic carbonates from CO2 and renewables

Nils Tenhumberg,^a   Hendrik Büttner,^a   Benjamin Schäffner,^b  Daniela Kruse,^b   Michael Blumenstein^c and   Thomas Werner*^a  

*Corresponding authors

^aLeibniz-Institut für Katalyse e. V. (LIKAT Rostock), Albert-Einstein-Str. 29 a, 18059 Rostock, Germany
E-mail: thomas.werner@catalysis.de

^bEvonik Industries AG, Paul-Baumann-Str. 1, 45772 Marl, Germany

^cHobum Oleochemicals, Seehafenstraße 20, 21079 Hamburg, Germany

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC00671J. http://pubs.rsc.org/en/Content/ArticleLanding/2016/GC/C6GC00671J?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Phosphonium salts and various (transition-) metals were studied as catalysts in the synthesis of carbonated oleochemicals from the corresponding epoxides and carbon dioxide. In combination with tetra-n-butylphosphonium bromide molybdenum compounds were identified as highly active co-catalysts for the formation of cyclic carbonates. The co-catalyst accelerates the conversion of the epoxidized fatty acid ester considerably.

The chemo- as well as the stereoselectivity of the carbonated oleochemicals can be controlled by the choice of the catalyst and the reaction conditions. Under optimized reaction conditions this new catalyst system allows the conversion of both mono- and polyepoxidized oleo compounds into the corresponding carbonates in good to excellent yields up to >99% under comparatively mild reaction conditions. This procedure has been applied to the synthesis of a potential renewable plasticizer and works well even at larger scale (200 g).

/////////Cooperative catalyst system, synthesis, oleochemical cyclic carbonates,  CO2, renewables