6816-17-7Relevant academic research and scientific papers
Switching the Reactivity of Palladium Diimines with “Ancillary” Ligand to Select between Olefin Polymerization, Branching Regulation, or Olefin Isomerization
Jones, Glen R.,Basbug Alhan, Hatice E.,Karas, Lucas J.,Wu, Judy I.,Harth, Eva
supporting information, p. 1635 - 1640 (2020/11/30)
Coordinating solvents are commonly employed as ancillary ligands to stabilize late transition metal complexes and are conventionally considered to have little effect on the reaction products. Our work identifies that the presence of ancillary ligand in Pd-diimine catalyzed polymerizations of α-olefins can drastically alter reactivity. The addition of different amounts of acetonitrile allows for switching between distinct reaction modes: isomerization–polymerization with high branching (0 equiv.), regular chain-walking polymerization (1 equiv.), and alkene isomerization with no polymerization (>20 equiv.). Optimization of the isomerization reaction mode led to a general set of conditions to switch a wide variety of diimine complexes into efficient alkene isomerization catalysts, with catalyst loading as low as 0.005 mol %.
Normal Alpha Olefin Synthesis Using Metathesis and Dehydroformylation
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, (2018/05/24)
The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, and 1-decene, in a multistep synthesis scheme. Generally, a first normal alpha olefin is subjected to an olefin metathesis step to form a linear internal olefin, which is then subjected to an isomerization-hydroformylation step to form a linear aldehyde, which is then subjected to a dehydroformylation step to form a second normal alpha olefin.
Careful investigation of the hydrosilylation of olefins at poly(ethylene glycol) chain ends and development of a new silyl hydride to avoid side reactions
Shin, Hyunseo,Moon, Bongjin
, p. 527 - 536 (2018/01/27)
Hydrosilylation of olefin groups at poly(ethylene glycol) chain ends catalyzed by Karstedt catalyst often results in undesired side reactions such as olefin isomerization, hydrogenation, and dehydrosilylation. Since unwanted polymers obtained by side reactions deteriorate the quality of end-functional polymers, maximizing the hydrosilylation efficiency at polymer chain ends becomes crucial. After careful investigation of the factors that govern side reactions under various conditions, it was related that the short lifetime of the unstable Pt catalyst intermediate led to the formation of more side products under the inherently dilute conditions for polymers. Based on these results, two new chelating hydrosilylation reagents, tris(2-methoxyethoxy)silane (5) and 2,10-dimethyl-3,6,9-trioxa-2,10-disilaundecane (6), have been developed. It was demonstrated that the hydrosilylation efficiency at polymer chain ends was significantly increased by employing the internally coordinating hydrosilane 5. In addition, employment of the internally coordinating disilane species 6 in an addition polymerization with 1,5-hexadiene by hydrosilylation reaction yielded a polymer with high molecular weight (Mn = 9300 g/mol), which was significantly higher than that (Mn = 2600 g/mol) of the corresponding polymer obtained with non-chelating dihydrosilane, 1,1,3,3-tetramethyldisiloxane.
Effect of the presence of ionic liquid during the NiMoS bulk preparation in the transformation of decanoic acid
Leyral, Géraldine,Brillouet, Soizic,Rousseau, Julie,Richard, Frédéric,Mamede, Anne Sophie,Courthéoux, Laurence,Pradel, Annie,Ribes, Michel,Brunet, Sylvette
, p. 120 - 132 (2017/01/11)
The impact of the presence and amount of [BMIM][NTf2] ionic liquid during the preparation of bulk NiMoS catalysts was investigated. It was clearly shown that these factors have a strong influence on both the morphology and specific surface area of the obtained NiMoS samples. Most interestingly the catalytic activity for the transformation of decanoic acid increased up to three times when IL was present during synthesis. In the same time, a greater selectivity towards hydrocarbons was observed. On the whole a clear relationship between catalytic activity, selectivity and NiMoS morphology was demonstrated. Consequently, it is possible to modify the morphology of the materials and impact the catalytic properties by changing the synthesis conditions.
Acid-catalysed carboxymethylation, methylation and dehydration of alcohols and phenols with dimethyl carbonate under mild conditions
Jin, Saimeng,Hunt, Andrew J.,Clark, James H.,McElroy, Con Robert
supporting information, p. 5839 - 5844 (2016/11/06)
Dimethyl carbonate (DMC) chemistry has been extended to include acid-catalysed reactions of different aliphatic alcohols and phenols. For the first time, p-toluenesulfonic acid (PTSA), H2SO4, AlCl3 and FeCl3 have been shown to aid carboxymethylation for primary aliphatic alcohols at catalytic loadings with quantitative conversion and selectivity. For carboxymethylation of secondary alcohols, stoichiometric PTSA and catalytic AlCl3 both gave quantitative conversion and selectivity. Stoichiometric FeCl3 and H2SO4 promoted dehydration of linear aliphatic alcohols. Additionally FeCl3 catalysed methylation of cyclohexanol, whilst AlCl3 resulted in methylation of phenolic compounds. This research expands the range of potential application for DMC in green chemistry.
METHODS OF MAKING FUNCTIONALIZED INTERNAL OLEFINS AND USES THEREOF
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Paragraph 00147-00148, (2014/06/23)
A method of isomerizing a substance includes combining a substance including a terminal alkenyl group and a substance including a fluorosulfonic acid group in a reaction mixture, and forming a substance including a 2-alkenyl group from the substance including a terminal alkenyl group in the reaction mixture. The method may be used to functionalize a substance, as the substance including a 2-alkenyl group can be reacted with a functionalizing agent to form a substance including a first functional group. The methods may be used to form a dicarboxylic acid, such as suberic acid, from a renewable feedstock.
Trial for anti-markovnikov hydration of 1-decene using platinum complexes bearing a pbp pincer ligand, inducing alkene isomerization and decomposition of PBP ligand
Ogawa, Hayato,Yamashita, Makoto
supporting information, p. 664 - 666 (2014/05/20)
Mixing of [(PBP)PtCl] complex with 1-decene and H2O afforded isomerized alkenes. Deuterium-labeling experiment indicated the catalytically active hydride species for alkene isomerization formed from water and [(PBP)Pt] complex. Reaction of [(PBP)PtNTf2] with H2O gave a platinum hydride complex having PNNP ligand with a loss of boron atom, but the resulting complex showed low catalytic activity. Two types of cationic platinum hydride complexes were suggested as active species for alkene isomerization.
Enantioselective synthesis of tertiary and quaternary stereogenic centers: Copper/phosphoramidite-catalyzed allylic alkylation with organolithium reagents
Fananas-Mastral, Martin,Perez, Manuel,Bos, Pieter H.,Rudolph, Alena,Harutyunyan, Syuzanna R.,Feringa, Ben L.
supporting information; experimental part, p. 1922 - 1925 (2012/04/17)
An efficient and highly enantioselective copper-catalyzed allylic alkylation of disubstituted allyl halides with primary and secondary organolithium reagents using phosphoramidite ligands is reported. The use of trisubstituted allyl bromides allows, for the first time, the enantioselective synthesis of all-carbon quaternary stereogenic centers with these reactive organometallic reagents.
Liquid phase alkylation of benzene with dec-1-ene catalyzed on supported 12-tungstophosphoric acid
Hernández-Cortez,Martinez,Soto,López,Navarrete,Manríquez,Lara,López-Salinas
scheme or table, p. 346 - 352 (2010/08/06)
The liquid phase alkylation of benzene with dec-1-ene was catalyzed by 12-tungstophosphoric acid (WP) supported on different solids (ZrO2, SiO2, activated carbon and boehmite-Al2O3). Catalysts prepared with 20 w
