20063-97-2Relevant articles and documents
Synthesis and catalytic activity of η1-allyl and η3-allyl, ethyl, and hydrido complexes of ruthenium- pentamethyl[60]fullerene
Matsuo, Yutaka,Uematsu, Takashi,Nakamura, Eiichi
, p. 2729 - 2733 (2007)
η1-Allyl and η3-allyl, ethyl, and hydrido ruthenium complexes of pentamethyl[60]fullerene, Ru(η5-C 60Me5)R(CO)2 (R = η1-allyl, Et, H) and Ru(η5-C60Me5)(η3- allyl)(CO) were synthesized by the reaction of a chlorido complex Ru(η5-C60Me5)Cl(CO)2 with an allyl and an ethyl Grignard reagent or lithium aluminum hydride. Conversion of the η1-allyl complex to the corresponding η3-allyl complex and the catalytic performance of the hydrido and the chlorido complexes in the isomerization reaction of 1-decene to internal decenes are described. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Isomerization of terminal alkenes by the Cp2TiCl2/Mg/BrCH2CH2Br system
Rao, S. Achyutha,Periasamy, M.
, p. 15 - 20 (1988)
The reagents prepared in situ in tetrahydrofuran (THF) by reaction of Cp2TiCl2 with isobutyl or t-butylmagnesium halides or with Grignard grade magnesium and 1,2-dibromomethane bring about isomerization of some 1-alkenes into trans-2-alkenes under mild conditions.
Kinetics of the Isomerization of 1-Decene to cis- and trans-2-Decene
Aimar, Mario L.,Rossi, Rita H. de
, p. 4255 - 4257 (1995)
-
Modular Ni(0)/Silane Catalytic System for the Isomerization of Alkenes
Chang, Alison Sy-Min,Cook, Amanda K.,Kawamura, Kiana E.,Martin, Daryl J.,Morris, Parker T.,Smith, Haley M.
supporting information, p. 486 - 496 (2022/03/02)
Alkenes are used ubiquitously as starting materials and synthetic targets in all areas of chemistry. Controlling their geometry and position along a chain is vital to their reactivity and properties yet remains challenging. Alkene isomerization is an atom-economical process to synthesize targeted alkenes, and selectivity can be controlled using transition metal catalysts. The development of mild, selective isomerization reactivity has enabled efficient tandem catalytic systems for the remote functionalization of alkenes, a process in which a starting alkene is isomerized to a new position prior to the functionalization step. The key challenges in developing isomerization catalysts for remote functionalization applications are (i) a lack of modularity in the catalyst structure and (ii) the requirement of nonmodular and/or harsh additives during catalyst activation. We address both challenges with a modular (NHC)Ni(0)/silane catalytic system (NHC, N-heterocyclic carbene), demonstrating the use of triaryl silanes and readily accessible (NHC)Ni(0) complexes to form the proposed active (NHC)(silyl)Ni-H species in situ. We show that modification of the steric and electronic nature of the catalyst via modification of the ancillary ligand and silane partner, respectively, is easily achieved, creating a uniquely versatile catalytic system that is effective for the formation of internal alkenes with high yield and selectivity for the E-alkene. The use of silanes as mild activators enables isomerization of substrates with a variety of functional groups, including acid-labile groups. The broad substrate scope, enabled by catalyst design, makes this catalytic system a strong candidate for use in tandem catalytic applications. Preliminary mechanistic studies support a Ni-H insertion/elimination pathway.
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
-
, (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.
