7642-09-3Relevant articles and documents
SYNTHESIS OF PHEROMONE DERIVATIVES VIA Z-SELECTIVE OLEFIN METATHESIS
-
Paragraph 0222; 0232, (2021/12/28)
Disclosed herein are methods for synthesizing fatty olefin metathesis products of high Z-isomeric purity from olefin feedstocks of low Z-isomeric purity. The methods include contacting a contacting an olefin metathesis reaction partner, such as acylated alkenol or an alkenal acetal, with an internal olefin in the presence of a Z-selective metathesis catalyst to form the fatty olefin metathesis product. In various embodiments, the fatty olefin metathesis products are insect pheromones. Pheromone compositions and methods of using them are also described.
Allylnickel(II) complexes of bulky 5-substituted-2-iminopyrrolyl ligands
Cruz, Tiago F. C.,Gomes, Pedro T.,Lopes, Patrícia S.
, (2021/08/05)
The optimized reaction between [Ni(COD)2] (COD = 1,5-cyclooctadiene) and ligand precursor 5-(2,4,6-triisopropylphenyl)-2-[N-(2,6-diisopropylphenyl)-formimino]-1H-pyrrole yielded the η3-cyclooctenyl-Ni(II) complex [Ni{κ2N,N’-5-(2,4,6-iPr3C6H2)-NC4H2-2-C(H) = N(2,6-iPr2C6H3)}(η3-C8H13)] 1. Subsequently, the η3-allyl complexes [Ni{κ2N,N’-5-R-NC4H2-2-C(H)=N(2,6-iPr2C6H3)}(η3-C3H5)] (R = 3,5-(CF3)2C6H3 (2a), 2,6-Me2C6H3 (2b), 2,4,6-iPr3C6H2 (2c) and CPh3 (2d)) were prepared in good yields via metathesis of [Ni(η3-C3H5)(μ-Br)]2 with the respective potassium 5-R-2-[N-(2,6-diisopropylphenyl)formimino]pyrrolyl salt (KLa-d). Complexes 1 and 2a-d were characterized by NMR spectroscopy, elemental analysis and complex 2d further analyzed by single crystal X-ray diffraction. Addition of excess pyridine to solutions of complexes 2a-d led to the observation of a fluxional process that, according to VT-NMR experiments, corresponds to a pyridine-assisted cis–trans isomerization process occurring in these complexes, via a η3-η1-η3 haptotropic shift of the allyl ligand, with ΔG? values in range of 9.5–17.3 kcal mol?1. Additionally, complexes 2a-d, when activated by B(C6F5)3, slowly catalyzed the isomerization of hex-1-ene to mixtures of internal olefins.
Bis(phosphine)hydridorhodacarborane Derivatives of 1,1′-Bis(ortho-carborane) and Their Catalysis of Alkene Isomerization and the Hydrosilylation of Acetophenone
Chan, Antony P. Y.,Parkinson, John A.,Rosair, Georgina M.,Welch, Alan J.
supporting information, (2020/02/04)
Deprotonation of [7-(1′-closo-1′,2′-C2B10H11)-nido-7,8-C2B9H11]- and reaction with [Rh(PPh3)3Cl] results in isomerization of the metalated cage and the formation of [8-(1′-closo-1′,2′-C2B10H11)-2-H-2,2-(PPh3)2-closo-2,1,8-RhC2B9H10] (1). Similarly, deprotonation/metalation of [8′-(7-nido-7,8-C2B9H11)-2′-(p-cymene)-closo-2′,1′,8′-RuC2B9H10]- and [8′-(7-nido-7,8-C2B9H11)-2′-Cp*-closo-2′,1′,8′-CoC2B9H10]- affords [8-{8′-2′-(p-cymene)-closo-2′,1′,8′-RuC2B9H10}-2-H-2,2-(PPh3)2-closo-2,1,8-RhC2B9H10] (2) and [8-(8′-2′-Cp*-closo-2′,1′,8′-CoC2B9H10)-2-H-2,2-(PPh3)2-closo-2,1,8-RhC2B9H10] (3), respectively, as diastereoisomeric mixtures. The performances of compounds 1-3 as catalysts in the isomerization of 1-hexene and in the hydrosilylation of acetophenone are compared with those of the known single-cage species [3-H-3,3-(PPh3)2-closo-3,1,2-RhC2B9H11] (I) and [2-H-2,2-(PPh3)2-closo-2,1,12-RhC2B9H11] (V), the last two compounds also being the subjects of 103Rh NMR spectroscopic studies, the first such investigations of rhodacarboranes. In alkene isomerization all the 2,1,8-or 2,1,12-RhC2B9 species (1-3, V) outperform the 3,1,2-RhC2B9 compound I, while for hydrosilylation the single-cage compounds I and V are better catalysts than the double-cage species 1-3.
