Mechanistic investigation in the [1,4] and [1,2] Wittig rearrangement reactions: a DFT study
文献情報
Shilpa R. Nath, Kaustubh A. Joshi
The mechanistic pathways for the [1,4] and [1,2] Wittig rearrangements of 2-silyl-6-aryl-5,6-dihydro-(2H)-pyrans have been studied at the M06-2X/6-31+G(d,p), 6-311++G(d,p) and cc-pVTZ level of theory. The crucial C–O bond cleavage step in the mechanism has been analysed initially, using two model reactions covering aliphatic as well as cyclic allylic ethers. The barriers for the one-step as well as two-step pathways have been calculated and the mechanisms for both the [1,4] and [1,2] Wittig rearrangement reactions are predicted to occur through a two-step mode. An energetic analysis of the reaction pathways reveals that the [1,4]-rearrangement has a lower barrier than the [1,2]-Wittig rearrangement. The C–O cleavage transition state was found to have the highest barrier and is thus the rate determining transition state for all of the studied molecules. This is in agreement with the previously published experimental studies. The role of the allylic trimethylsilane group in the stabilization of the intermediate anions of the Wittig reactants has also been investigated while comparing it with the phenyl and allylic t-butyl groups through Natural Bond Orbital (NBO) calculations.
関連文献
FTIR spectroscopy of carbon dioxide adsorbed on sodium- and magnesium-exchanged ETS-10 molecular sieves
F. X. Llabrés i Xamena, A. Zecchina
DOI: 10.1039/B110483G
Secondary quasiperiodicity in the peroxidase–oxidase reaction
Lars F. Olsen, Tatiana V. Bronnikova, William M. Schaffer
DOI: 10.1039/B107311G
UV/Vis/near-IR spectroscopic characteristics of H4−xCsxPVMo11O40 (x = 0, 2) catalyst under different temperatures and gas atmospheres
J. Melsheimer, J. Kröhnert, R. Ahmad, S. Klokishner, F. C. Jentoft, G. Mestl, R. Schlögl
DOI: 10.1039/B109293F
The spectroscopy of Rydberg to Rydberg transitions in I2 and Br2 investigated by vibrationally induced autoionization
Martin C. R. Cockett, David A. Beattie, Neil A. Macleod, Kenneth P. Lawley, Trevor Ridley, Robert J. Donovan
DOI: 10.1039/B109560A
Transformation of diamond nanoparticles into carbon onions under electron irradiation
V. V. Roddatis, V. L. Kuznetsov, Yu. V. Butenko, D. S. Su, R. Schlögl
DOI: 10.1039/B110487J
Gibbs energy of solvation of organic ions in aqueous and dimethyl sulfoxide solutions
Josefredo R. Pliego Jr, José M. Riveros
DOI: 10.1039/B109595A
Mechanistic studies on the bromate–1,4-cyclohexanedione–ferroin oscillatory system
István Szalai, Krisztina Kurin-Csörgei, Miklós Orbán
DOI: 10.1039/B109388F
Time-resolved dual fluorescence of 1-phenylpyrrole in acetonitrile: molecular dynamics simulations of solvent response to twisted intramolecular charge transfer
Jörn Manz, Boris Proppe, Burkhard Schmidt
DOI: 10.1039/B109488B
こちらもおすすめ
4-アミノフェノール酸ナトリウム水和物とは何ですか?
4-アミノフェノール酸ナトリウム水和物は、CAS番号206557-08-6の化合物で、4-アミノフェノールとナトリウムが結合した塩と水和物です。この化合物は、白...
Methyl 3-methyl-N-{[(2-methyl-2-propanyl)oxy]carbonyl}-L-histidinateの代替品はありますか?
この化合物は特定の合成プロセスに使用される可能性がありますが、代替品として、他の类似的な化合物、例えばMethyl 3-methyl-N-{[(2-methyl...
4-Boc-2-哌嗪甲酸の市場動向や研究トレンドはどうですか?
4-Boc-2-哌嗪甲酸は、薬品開発や合成化学分野で広く使用されており、その需要は継続的に推移しています。特に、新薬開発における合成化学分野での需要が高まってい...
4,4'-二羟甲基联苯の物理化学的性質は何ですか?
4,4'-二羟甲基联苯のCAS番号は1667-12-5です。この化合物は白色の結晶粉末で、分子量は154.20です。水にわずかに溶けますが、アルコールや有機溶媒...
5-甲硫基戊腈はどの業界で使用されていますか?
5-甲硫基戊腈は医薬品産業で使用される可能性があります。また、ポリマー合成の触媒として、センサー製造の一部として、半導体製造のプロセス改善に使用される可能性があ...
CAS番号1311961-50-8の化合物はどのように合成されますか?
この化合物は、1-abieta-8,11,13-trien-19-イルと6'-メトキシシンコナナン-9-基を含有する窒素含有化合物から合成されます。一般的な合成...
6-ブロモベンジジミダゾール-2-カルビルデオキシドはどのように保存すればよいですか?
6-ブロモベンジジミダゾール-2-カルビルデオキシドは、避光・乾燥した容器(密閉容器)で-20℃~4℃の低温で保存してください。高温や直射日光、湿気は避けてくだ...
Boc-N-甲基氨甲环酸とは何ですか?
621-65-8のCAS番号を持つBoc-N-甲基氨甲环酸は、化学式C7H13NO5を有する化合物です。この化合物は白色の結晶性粉末で、吸湿性があります。
乙基三氟硼酸钾はどのように合成されますか?
乙基三氟硼酸钾は、トリフLUオール酸カリウムとエチルブロミドを反応させて合成されます。この反応は高い選択性と収率を持ち、触媒を用いることで効率的に進行します。
2-フロウロ-5-クロロ-4-アミノフェノールはどのように保存すればよいですか?
2-フロウロ-5-クロロ-4-アミノフェノールは、直射日光を避けて冷却された暗所で保存し、密閉容器に保管してください。温度は常温か低温が適しています。
掲載誌
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.














