Catalytic Dimerization of Acrylonitrile

Kashiwagi, Kohichi; Sugise, Ryoji; Shimakawa, Toshihiro; Matuura, Tunao; Shirai, Masato; Kakiuchi, Fumitoshi; Murai, Shinji

doi:10.1021/om970263a

Cited by 51 publications

(22 citation statements)

References 8 publications

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“…139 Arginine can be used to produce 1,4-diaminobutane via hydrolysis to ornithine and subsequent decarboxylation. Acrylonitrile can also dimerised to from adiponitrile, 144 or hydrated to form acrylamide. Aspartic acid can be alpha-decarboxylated to form beta-alanine by the use of aspartate alpha-decarboxylase, an intermediate that could be used for the synthesis of acrylamide.…”

Section: Bio-and Organocatalysismentioning

confidence: 99%

Deoxygenation of biobased molecules by decarboxylation and decarbonylation – a review on the role of heterogeneous, homogeneous and bio-catalysis

et al. 2015

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Use of biomass is crucial for a sustainable supply of chemicals and fuels for future generations. Compared to fossil feedstocks, biomass is more functionalized and requires defunctionalisation to make it suitable for use. Deoxygenation is an important method of defunctionalisation. While thermal deoxygenation is possible, high energy input and lower reaction selectivity makes it less suitable for producing the desired chemicals and fuels. Catalytic deoxygenation is more successful by lowering the activation energy of the reaction, and when designed correctly, is more selective. Catalytic deoxygenation can be performed in various ways. Here we focus on decarboxylation and decarbonylation. There are several classes of catalysts: heterogeneous, homogeneous, bio-and organocatalysts and all have limitations. Homogeneous catalysts generally have superior selectivity and specificity but separation from the reaction is cumbersome. Heterogeneous catalysts are more readily isolated and can be utilised at high temperatures, however they have lower selectivity in complex reaction mixtures. While bio-catalysts can operate at ambient temperatures, the volumetric productivity is lower. Therefore it is not always apparent in advance which catalyst is the most suitable in terms of conversion and selectivity under optimal process conditions. Here we compare classes of catalysts for the decarboxylation and decarbonylation of biobased molecules and discuss their limitations and advantages. We mainly focus on the activity of the catalysts and find there is a strong correlation between specific activity (turn over frequency) and temperature for metal based catalysts (homogeneous or heterogeneous). Thus one is not more active than the other at the same temperature. Alternatively, enzymes have a higher turnover frequency but drawbacks (low volumetric productivity) should be overcome.

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Section: Bio-and Organocatalysismentioning

confidence: 99%

Deoxygenation of biobased molecules by decarboxylation and decarbonylation – a review on the role of heterogeneous, homogeneous and bio-catalysis

et al. 2015

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“…In several cases, however, the linkage isomerization is accompanied by a rearrangement in the geometry of the complex (Scheme 53), such as in cis,fac-RuCl 2 (dmso-S) 3 (dmso-O) (8) vs trans-RuCl 2 (dmso-S) 4 (9), 54 4 (36). 369,370,372 In some cases, the linkage/geometrical isomers are apparently not in equilibrium, and they derive either from different precursors or from the same precursor by different synthetic procedures: see for example cis,cis,cis-RuCl 2 (dmso-S)(dmso-O)(CO) 2 (27), cis,trans, cis-RuCl 2 (dmso-S) 2 (CO) 2 (28), and trans,cis,cis-RuCl 2 -(dmso-O) 2 (CO) 2 (34) (Schemes 44 and 46). 336 There are instead relatively few examples concerning pure linkage isomers, in which the S/O isomerization leaves the rest of the complex unchanged.…”

Section: S/o Linkage Isomerizationmentioning

confidence: 99%

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

2004

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“…that the isomers of 1,4-dicyanobutadiene were obtained experimentally, but, to the best of our knowledge, they have not been used in Diels-Alder reactions. [12] The most salient of these results are gathered in Table 1, which highlights their dramatic dependency on the nature of the reactants.…”

Section: Addition Of Acrylonitrile (11) and Fluoroethylene (15) To (Ementioning

confidence: 98%

Diels–Alder Reactions of Symmetrically 1,4‐Disubstituted Dienes: Theoretical Study on the Influence of the Configuration of the Double Bonds on the Regio‐ and Endoselectivity

et al. 2008

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It was experimentally shown in Diels‐Alder reactions that symmetrically 1,4‐disubstituted dienes exhibit high regio‐ and endoselectivity induced by the (E,Z) configuration of the double bonds. In order to understand the origin of this selectivity, the transition states associated with the reaction between a series of such dienes (R = OMe, CH3, NH2, F, CN) on substituted ethylene (R′ = CO2Me, CN, F, OMe) were determined by DFT calculations. If the regioselectivity confirmed by a single‐point MP2 calculation is predicted to be good in most cases, its direction remains difficult to predict; the R′ group of the dienophile can orient itself toward either the (Z) or the (E) side of the diene. Neither primary nor secondary frontier orbital interactions appear to be able to rationalize these results. They are more likely explained by a delicate balance between steric and electrostatic interactions. This hypothesis is further supported by the calculated reactivity of the (E,E) and (Z,Z) corresponding dienes. In any case, a standard DFT calculation, confirmed by a single‐point MP2 step, is likely to provide a reliable guideline for a synthesis strategy that allows the control of up to four stereogenic centres in a single reaction step.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Catalytic Dimerization of Acrylonitrile

Cited by 51 publications

References 8 publications

Deoxygenation of biobased molecules by decarboxylation and decarbonylation – a review on the role of heterogeneous, homogeneous and bio-catalysis

Deoxygenation of biobased molecules by decarboxylation and decarbonylation – a review on the role of heterogeneous, homogeneous and bio-catalysis

Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

Diels–Alder Reactions of Symmetrically 1,4‐Disubstituted Dienes: Theoretical Study on the Influence of the Configuration of the Double Bonds on the Regio‐ and Endoselectivity

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