21181-46-4Relevant academic research and scientific papers
Beyond Takai's Olefination Reagent: Persistent Dehalogenation Emerges in a Chromium(III)-μ3-Methylidyne Complex
Anwander, Reiner,Langmann, Jan,Maichle-M?ssmer, C?cilia,Scherer, Wolfgang,Trzmiel, Simon,Werner, Daniel
supporting information, p. 20049 - 20054 (2021/08/06)
Reaction of CHI3 with six equivalents of CrCl2 in THF at low temperatures affords [Cr3Cl3(μ2-Cl)3(μ3-CH)(thf)6] as the first isolable high-yield CrIII μ3-methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali-metal cyclopentadienides generates isostructural half-sandwich chromium(III)-μ3-methylidynes [CpR3Cr3(μ2-Cl)3(μ3-CH)] (CpR=C5H5, C5Me5, C5H4SiMe3). Side and decomposition products of the Cl/CpR exchange reactions were identified and structurally characterized for [Cr4(μ2-Cl)4(μ2-I)2(μ4-O)(thf)4] and [(η5-C5H4SiMe3)CrCl(μ2-Cl)2Li(thf)2]. The Cl/CpR exchange drastically changed the ambient-temperature effective magnetic moment μeff from 9.30/9.11 μB (solution/solid) to 3.63/4.32 μB (CpR=C5Me5). Reactions of [Cr3Cl3(μ2-Cl)3(μ3-CH)(thf)6] with aldehydes and ketones produce intricate mixtures of species through oxy/methylidyne exchange, which were partially identified as radical recombination products through GC/MS analysis and 1H NMR spectroscopy.
STERICALLY SCREENED HALOGENOCYCLOBUTANONES. IX. 2-SUBSTITUTED METHYLENECYCLOPROPANES IN REACTION WITH DICHLOROKETENE
Bessmertnykh, A. G.,Grishin, Yu. K.,Donskaya, N. A.,Karpov, M. V.,Kisina, M. Yu,et al.
, p. 94 - 99 (2007/10/02)
The reaction of methylenecyclopropanes containing donating substituents at position 2 of the three-membered ring with dichloroketene leads to the exclusive formation of 4,4-dichlorospirohexan-5-ones.The presence of a methoxycarbonyl group in the small ring leads to the formation of the two regioisomers of spirohexanone.The initially formed adduct of 2,2-dicyclopropyl-1-methylenecyclopropane with dichloroketene undergoes a rearrangement under the reaction conditions, leading to 2-chloro-3-(5-chloro-2-cyclopropyl-2-pentenyl)cyclobut-2-en-1-one.
