Improved Reaction and Activation Energies of [4+2] Cycloadditions,[3,3] Sigmatropic Rearrangements and Electrocyclizations with the Spin-Component-Scaled MP2 Method

T.P.M.Goumans; Andreas W.Ehlers; Koop Lammertsma

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Improved Reaction and Activation Energies of [4+2] Cycloadditions,[3,3] Sigmatropic Rearrangements and Electrocyclizations with the Spin-Component-Scaled MP2 Method

机译：自旋组分定标的MP2方法改进了[4 + 2]环加成，[3,3]适性重排和电环化的反应和活化能

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A new quantum mechanical scheme to calculate electronic correlation energies,spin-component-scaled MP2,was tested as a tool to predict reaction energies and barriers in computational organic chemistry.Three common pericyclic reactions with known unsatisfactory MP2 descriptions were reinvestigated with the modified MP2 approach,in which the parallel and anti-parallel spin components of the correlation energy are scaled sepa-rately.The SCS-MP2 calculated reaction and activation energies of nine Diels-Alder reactions,four [3,3] sigma-tropic rearrangements,and ten electro-cyclization reactions are compared to those of the MP2,B3LYP,QCISD(T),and G3 methods.For each,the SCS-MP2 results are in excellent agreement with the experimental data and compare far more favorably to G3 than both MP2 and B3LYP.Careful evaluation of the effect of the size of the atomic orbital(AO)basis set shows that the larger expansions improve the agreement with experiment for the SCS-MP2 method,while they get worse for both MP2 and B3LYP.

机译：测试了一种新的计算电子相关能的量子力学方案，即自旋比例缩放的MP2，作为预测计算有机化学中反应能和势垒的工具。使用改进的MP2方法对三种已知的MP2描述欠佳的常见环周反应进行了重新研究SCS-MP2计算出九个Diels-Alder反应，四个[3,3]σ重排和十个Diels-Alder反应的反应和活化能，分别对相关能量的平行和反平行自旋分量进行缩放。将电环化反应与MP2，B3LYP，QCISD（T）和G3方法进行了比较.SCS-MP2的每种结果与实验数据均非常吻合，并且与MP2和MP3相比，与G3的对比更有利B3LYP。对原子轨道（AO）基集的影响的仔细评估表明，较大的扩展改善了与SCS-MP2方法实验的一致性，但扩展性却越来越差或同时使用MP2和B3LYP。

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《Chemistry: A European journal》 |2004年第24期|共8页
作者
T.P.M.Goumans; Andreas W.Ehlers; Koop Lammertsma;
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正文语种 eng
中图分类化学;
关键词
ab initio calculations; Cope rearrangement; Diels-Alder reaction; electroeyclization reaction; heterocycles; pericyclic reaction;

机译：从头算;应付重排;Diels-Alder反应;电化反应;杂环;周环反应;

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1. Improved Reaction and Activation Energies of [4+2] Cycloadditions,[3,3] Sigmatropic Rearrangements and Electrocyclizations with the Spin-Component-Scaled MP2 Method [J] . T.P.M.Goumans, Andreas W.Ehlers, Koop Lammertsma Chemistry: A European journal . 2004,第24期

机译：自旋组分定标的MP2方法改进了[4 + 2]环加成，[3,3]适性重排和电环化的反应和活化能
2. An Yb(OTf)(3)and visible light relay catalyzed [3+2] cycloaddition/[3,3]-rearrangement/[4+2] cycloaddition in one pot to prepare oxazonine-fused endoperoxides [J] . Green chemistry . 2020,第12期

机译：Yb（OTF）（3）和可见光继电器催化[3 + 2]环加成/ [3,3] - 再rangement / [4 + 2]环加成在一个锅中制备恶唑胺融合的内末氧化酯
3. Synthetic Route to 4,4a‐ and 3,4‐Dihydroxanthones through [4+2] Cycloaddition and Base‐Assisted Sigmatropic Rearrangement [J] . Chernov Nikita M., Shutov Roman V., Sharoyko Vladimir V., European journal of organic chemistry . 2017,第19期

机译：通过[4 + 2]环加入和基础辅助的Sigmatropic重排，合成途径至4,4a-和3,4-二羟基吡啶
4. Stereoselective 3,3-Sigmatropic Rearrangement Utilizing Binuclear alpha,beta-Unsaturated Fischer Carbene Complexes with Planar Chiral (Arene)chromium Complex [C] . Ken Kamikawa, Yasunori Shimizu, Atsushi Tachibana, Symposium on Organometallic Chemistry . 2004

机译：立体选择性3,3 - 利用Binuclearα，Beta-Unsturated Fischer Carbene络合物与平面手性（芳烃）铬复合物
5. Titanium-mediated cyclization reactions: I. New synthetic methods for alkaloids. II. [1,3]- and [3,3]-sigmatropic rearrangements of vinylcyclobutanols [D] . Kim, Se-Ho 2002

机译：钛介导的环化反应：I.生物碱的新合成方法。二。乙烯基环丁醇的[1,3]-和[3,3]-σ重排
6. A thermally-induced tandem 33-sigmatropic rearrangement/2 + 2 cycloaddition approach to carbocyclic spirooxindoles [O] . Kay M Brummond, Joshua M Osbourn 2010

机译：热诱导串联33-σ重排/ 2 + 2环加成法合成碳环螺氧并吲哚
7. Activation Energies of Pericyclic Reactions: Performance of DFT, MP2, and CBS-QB3 Methods for the Prediction of Activation Barriers and Reaction Energetics of 1, 3-Dipolar Cycloadditions, and Revised Activation Enthalpies for a Standard Set of Hydrocarbon Pericyclic Reactions [O] . -1

机译：近期反应的激活能量：DFT，MP2和CBS-QB3的性能，用于预测1,3-偶极环加成的活化屏障和反应能量，以及用于标准烃近环反应的检测活化焓
8. Cycloaddition and Oxygen-Transfer Reactions of 2-(Trifluoromethyl)-3,3-difluorooxaziridine [R] . O'Brien, B. A., Lam, W. Y., DesMarteau, D. D. 1986

机译：2-（三氟甲基）-3,3-二氟恶唑啶的环加成反应和氧转移反应

Improved Reaction and Activation Energies of [4+2] Cycloadditions,[3,3] Sigmatropic Rearrangements and Electrocyclizations with the Spin-Component-Scaled MP2 Method

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