Quantum chemical investigation of the thermal rearrangement of cis- and trans-pinane
文献信息
Daniel Kinzel, Achim Stolle, Bernd Ondruschka, Leticia González
The thermal rearrangement reactions of cis-pinane, 1, and trans-pinane, 2, into β-citronellene, 3, and isocitronellene, 4, have been investigated using ab initio multiconfigurational CASSCF and CASSCF MP2 calculations. Concerted as well as stepwise retro-[2+2]-cycloaddition conversion mechanisms are discussed and the corresponding stationary points along the relevant reaction paths from the bicyclic starting compounds into their acyclic isomers have been optimized. Our calculations show that the stepwise retro-[2+2]-cycloaddition via biradicals is energetically favoured with respect to the concerted mechanism. In the biradical pathways to 3 and 4, it was found that a gauche ring opening of the cyclobutane ring in 1 and 2, respectively, shows significantly lower activation barriers than the competing anti ring opening. With the predicted reaction paths, the calculated activation energies are in very good agreement with experimental values. The reaction mechanisms can explain the differences in the reactivity of 1 and 2, as well as the selectivity differences with respect to the formation of 3 and 4, reported in previous kinetic studies.
相关文献
pH-Controlled twisted intramolecular charge transfer (TICT) excited state via changing the charge transfer direction
Guang-Jiu Zhao, Ke-Li Han
DOI: 10.1039/B924549A
Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations
Samar G. Moussa, Barbara J. Finlayson-Pitts
DOI: 10.1039/C000447B
Six-dimensional dynamics study of reactive and non reactive scattering of H2 from Cu(111) using a chemically accurate potential energy surface
C. Díaz, R. A. Olsen, D. J. Auerbach, G. J. Kroes
DOI: 10.1039/C001956A
Differences in structure, energy, and spectrum between neutral, protonated, and deprotonated phenol dimers: comparison of various density functionals with ab initio theory
Maciej Kołaski, Anupriya Kumar, N. Jiten Singh, Kwang S. Kim
DOI: 10.1039/C003008B
Formation of O adatom pairs and charge transfer upon O2 dissociation on reduced TiO2(110)
Yingge Du, Nathaniel A. Deskins, Zhenrong Zhang, Zdenek Dohnalek, Michel Dupuis, Igor Lyubinetsky
DOI: 10.1039/C000250J
Ab initio molecular dynamics simulations investigating proton transfer in perfluorosulfonic acid functionalized carbon nanotubes
Bradley F. Habenicht, Stephen J. Paddison, Mark E. Tuckerman
DOI: 10.1039/C0CP00130A
Origin of chiral selectivity in gas-phase serine tetramers
Anthony B. Costa, R. Graham Cooks
DOI: 10.1039/C0CP01402H
Enhanced performance of a dye-sensitized solar cell with the incorporation of titanium carbide in the TiO2 matrix
Chuan-Pei Lee, Po-Yen Chen, R. Vittal
DOI: 10.1039/B923477B
您可能还喜欢
4-[[6-(3-苯基苯基)-7H-嘌呤-2-基]氨基]苯磺酰胺(CAS号:2079895-42-2)适用哪些法规指南?
该化合物需遵循REACH法规以确保其安全使用和管理。同时,根据其潜在的生物降解性和毒性,也需要符合GHS分类中的相应要求。此外,若用于医药或食品相关领域,则还需...
反式-度骨化醇(CAS号:74007-20-8)的物理化学性质是什么?
反式-度骨化醇是一种脂溶性维生素D3的衍生物,呈无色或白色结晶性粉末,不溶于水,溶于乙醇、丙酮、氯仿等有机溶剂。其分子式为C28H44O,分子量为404.65。...
莲花掌苷(CAS号:59282-56-3)的市场或研究趋势如何?
莲花掌苷作为一种天然产物,近年来在抗炎、抗癌等生物活性研究方面显示出一定的潜力,因此市场需求逐渐增长。市场动态方面,随着天然产物开发的深入,预计该化合物的研究会...
2-溴-6-(吡咯烷-1-基)吡啶-4-硼酸频那醇酯(CAS号:1150271-64-9)应用于哪些行业?
2-溴-6-(吡咯烷-1-基)吡啶-4-硼酸频那醇酯在医药领域有着广泛的应用,它可以用作药物合成中的中间体。此外,它还可以用于有机合成,特别是在构建复杂杂环化合...
什么是methyl 2-(4-bromophenyl)-3-methylbutanoate(CAS号:1061284-70-5)?
methyl 2-(4-溴苯基)-3-甲基丁酸甲酯是一种化学物质,分子式为C12H13BrO2。它是一种有机化合物,具有一定的挥发性和易燃性。
CJC1-295(CAS号:863288-34-0)的物理化学性质是什么?
CJC1-295是一种具有复杂肽链结构的化合物,其分子量约为1875 Da。该化合物在水中具有一定的溶解性,但在有机溶剂中的溶解性不佳。它是一种反应活性化合物,...
三正丁基锍碘(CAS号:18146-62-8)的市场或研究趋势如何?
三正丁基锍碘作为一种重要的有机硫化合物,主要用于有机合成中作为亲电试剂。近年来,由于其在合成中的广泛应用,市场对其需求持续增长。此外,随着绿色化学的发展,对其替...
雌二醇-[13C3]同位素内标(CAS号:1261254-48-1)通常如何合成?
雌二醇-[13C3]同位素内标通常通过在雌二醇分子中引入[13C3]同位素来合成。常见的方法是通过化学标记反应,如与[13C3]标记的甲基溴化物进行亲核取代反应...
N1-(2-吡啶甲基)-N2-(2-甲基-1-萘基)草酰胺(CAS号:2611225-93-3)的物理化学性质是什么?
N1-(2-吡啶甲基)-N2-(2-甲基-1-萘基)草酰胺为固体化合物,具有良好的结晶形态,分子量为340.34 g/mol。该化合物在水中的溶解度较低,但在有...
如何处理含有十五碳烯酸甲酯(顺-10)(C15:1)标准品(CAS号:90176-52-6)的废料?
含有十五碳烯酸甲酯(顺-10)(C15:1)标准品的废料应首先进行适当收集和储存,避免与其他化学品混合。然后,可采用焚烧或交由专业废物处理公司进行处理。处理过程...
来源期刊
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














![2-Methyl-2-propanyl {3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3-oxetanyl}carbamate structure 2-Methyl-2-propanyl {3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3-oxetanyl}carbamate structure](https://cnstatic.chemtradehub.com/structs/127/1279090-25-3-1b84.webp)