1165952-92-0Relevant articles and documents
Thermal Reactions and Vibrational Spectra of 1,1-Dimethyl-1-silacyclobutane and 1,1,3,3-Tetramethyl-1,3-disilacyclobutane
Kalasinsky, V. F.,Pechsiri, S.
, p. 5110 - 5115 (1982)
Some thermal reactions involving 1,1-dimethyl-1-silacyclobutane have been studied by using conventional vacuum pyrolysis techniques and by using infrared laser radiation.The pyrolysis of 1,1-dimethyl-1-silacyclobutane is known to produce 1,1,3,3-tetramethyl-1,3-disilacyclobutane in nearly quantitative yields at 490 deg C.It has been found that 1,1,3,3-tetramethyl-1,3-disilacyclobutane can also be produced from 1,1-dimethyl-1-silacyclobutane by the adsorption of infrared laser radiation in the region between 1000 and 900 cm-1.The infrared and Raman spectra of the product have been recorded, and, on the basis of a complete vibrational assigment, the structure of 1,1,3,3-tetramethyl-1,3-disilacyclobutane appears to be one in which the ring assumes a planar configuration.Both 1,1-dimethyl-1-silacyclobutane and 1,1,3,3-tetramethyl-1,3-disilacyclobutane react with hydrogen chloride to produce trimethylchlorosilane.The mechanism of these reactions and the effects of varying reaction conditions are discussed.
The first metal complexes containing the 1,4-cyclohexa-2,5-dienyl ligand (benzene 1,4-dianion); synthesis and structures of [K(18-crown-6)][Ln{η5-C5H3(SiMe 3)2-1,3}2(C6H6
Cassani, M. Cristina,Gun'ko, Yurii K.,Hitchcock, Peter B.,Lappert, Michael F.
, p. 1987 - 1988 (1996)
The reaction of [Ln{η5-C5H3(SiMe3) 2-1,3}3] or [(Ln{η5-C5H3(SiMe3) 2-1,3}2(μ-Cl))2] (Ln = La, Ce) with K or Csu
Cimarusti,Wolinsky
, p. 113 (1968)
Catalytic carbonylative rearrangement of norbornadiene via dinuclear carbon-carbon oxidative addition
Hartline, Douglas R.,Zeller, Matthias,Uyeda, Christopher
, p. 13672 - 13675 (2017)
Single bonds between carbon atoms are inherently challenging to activate using transition metals; however, ring-strain release can provide the necessary thermodynamic driving force to make such processes favorable. In this report, we describe a strain-induced C-C oxidative addition of norbornadiene. The reaction is mediated by a dinuclear Ni complex, which also serves as a catalyst for the carbonylative rearrangement of norbornadiene to form a bicyclo[3.3.0] product.
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Chan,J.H.-H.,Rickborn,B.
, p. 6406 - 6411 (1968)
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Rhodium(I)-Catalyzed Enantioselective C(sp3)—H Functionalization via Carbene-Induced Asymmetric Intermolecular C—H Insertion?
Liu, Bo,Xu, Ming-Hua
supporting information, p. 1911 - 1915 (2021/05/31)
Transition-metal-catalyzed C—H insertion of metal-carbene represents an excellent and powerful approach for C—H functionalization. However, despite remarkable advances in metal-carbene chemistry, transition metal catalysts that are capable of enantioselective intermolecular carbene C—H insertion are mainly constrained to dirhodium(II) and iridium(III)-based complexes. Herein, we disclose a new version of asymmetric carbene C—H insertion reaction with rhodium(I) catalyst. A highly enantioselective rhodium(I) complex-catalyzed C(sp3)—H functionalization of 1,4-cyclohexadienes with α-aryl-α-diazoacetates was successfully developed. By using chiral bicyclo[2.2.2]-octadiene as ligand, rhodium(I)-carbene-induced asymmetric intermolecular C—H insertion proceeds smoothly at room temperature, allowing access to a diverse variety of α-aryl-α-cyclohexadienyl acetates and gem-diaryl-containing acetates in good yields with good to excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the reaction was highlighted by facile synthesis of a novel cannabinoid CB1 receptor ligand. This method may offer a new opportunity for the development of therapeutically exploitable cannabinoid receptor type ligands in medicinal chemistry.
Organocatalyzed Birch Reduction Driven by Visible Light
Cole, Justin P.,Chen, Dian-Feng,Kudisch, Max,Pearson, Ryan M.,Lim, Chern-Hooi,Miyake, Garret M.
supporting information, p. 13573 - 13581 (2020/09/03)
The Birch reduction is a powerful synthetic methodology that uses solvated electrons to convert inert arenes to 1,4-cyclohexadienes - valuable intermediates for building molecular complexity. Birch reductions traditionally employ alkali metals dissolved in ammonia to produce a solvated electron for the reduction of unactivated arenes such as benzene (Ered -3.42 V vs SCE). Photoredox catalysts have been gaining popularity in highly reducing applications, but none have been reported to demonstrate reduction potentials powerful enough to reduce benzene. Here, we introduce benzo[ghi]perylene imides as new organic photoredox catalysts for Birch reductions performed at ambient temperature and driven by visible light from commercially available LEDs. Using low catalyst loadings (1 mol percent), benzene and other functionalized arenes were selectively transformed to 1,4-cyclohexadienes in moderate to good yields in a completely metal-free reaction. Mechanistic studies support that this unprecedented visible-light-induced reactivity is enabled by the ability of the organic photoredox catalyst to harness the energy from two visible-light photons to affect a single, high-energy chemical transformation.
One-pot Synthesis of 1,3-Butadiene and 1,6-Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions
Turczel, Gábor,Kovács, Ervin,Csizmadia, Eszter,Nagy, Tibor,Tóth, Imre,Tuba, Robert
, p. 4884 - 4891 (2018/09/25)
A novel tandem reaction of cyclopentadiene leading to high value linear chemicals via ruthenium catalyzed ring opening cross metathesis (ROCM), followed by cross metathesis (CM) is reported. The ROCM of cyclopentadiene (CPD) with ethylene using commercially available 2nd gen. Grubbs metathesis catalysts (1-G2) gives 1,3-butadiene (BD) and 1,4-pentadiene (2) (and 1,4-cyclohexadiene (3)) with reasonable yields (up to 24 % (BD) and 67 % (2+3) at 73 % CPD conversion) at 1–5 mol % catalyst loading in toluene solution (5 V% CPD, 10 bar, RT) in an equilibrium reaction. The ROCM of CPD with cis-butene diol diacetate (4) using 1.00 - 0.05 mol % of 3rd gen. Grubbs (1-G3) or 2nd gen. Hoveyda-Grubbs (1-HG2) catalysts loading gives hexa-2,4-diene-1,6-diyl diacetate (5), which is a precursor of 1,6-hexanediol (an intermediate in polyurethane, polyester and polyol synthesis) and hepta-2,5-diene-1,7-diyl diacetate (6) in good yield (up to 68 % or TON: 1180). Thus, convenient and selective synthetic procedures are revealed by ROCM of CPD with ethylene and 4 leading to BD and 1,6-hexanediol precursor, respectively, as key components of commercial intermediates of high-performance materials.
