立体选择性亲核取代反应的动态起源。
Dynamic origin of the stereoselectivity of a nucleophilic substitution reaction.
机构信息
Department of Chemistry, Texas A&M University , PO Box 30012, College Station, Texas 77842, United States.
出版信息
Org Lett. 2012 May 18;14(10):2528-31. doi: 10.1021/ol300817a. Epub 2012 Apr 27.
Abstract
A nucleophilic substitution on a dichlorovinyl ketone was studied experimentally and computationally. A mixture of products is observed experimentally, but a conventional computational analysis does not account for the formation of the minor stereoisomer. Instead, the product mixture is predicted accurately from a dynamic trajectory study on a bifurcating energy surface. The dynamic origin of the stereoselectivity of the reaction is discussed.
摘要
对二氯代乙烯酮的亲核取代进行了实验和计算研究。实验中观察到了产物的混合物，但传统的计算分析并没有考虑到次要立体异构体的形成。相反，从分叉能面上的动态轨迹研究准确地预测了产物混合物。讨论了反应立体选择性的动力学起源。
相似文献
1
Dynamic origin of the stereoselectivity of a nucleophilic substitution reaction.立体选择性亲核取代反应的动态起源。
Org Lett. 2012 May 18;14(10):2528-31. doi: 10.1021/ol300817a. Epub 2012 Apr 27.
2
Regiodivergent halogenation of (E)-β-chlorovinyl ketones via soft α-vinyl enolization strategy.（E）-β-氯代乙烯基酮的区域发散卤化反应通过软α-乙烯基烯醇化策略实现。
Org Lett. 2015 Feb 6;17(3):450-3. doi: 10.1021/ol5034354. Epub 2015 Jan 27.
3
Modular construction of 2-substituted benzo[b]furans from 1,2-dichlorovinyl ethers.1,2-二氯乙烯基醚合成 2-取代苯并[b]呋喃的模块化构建。
Org Lett. 2009 Dec 3;11(23):5478-81. doi: 10.1021/ol902307m.
4
Stereoselective C9 arylation and vinylation of Cinchona alkaloids.金鸡纳生物碱的立体选择性C9芳基化和乙烯基化反应。
Org Lett. 2008 Feb 7;10(3):385-8. doi: 10.1021/ol7026625. Epub 2008 Jan 8.
5
Facial selectivity in the nucleophilic additions of vinylmagnesium bromide to bicyclo[2.2.2]oct-5-en-2-one derivatives.溴化乙烯基镁对双环[2.2.2]辛-5-烯-2-酮衍生物亲核加成反应中的面选择性
J Org Chem. 2007 Oct 12;72(21):7992-8004. doi: 10.1021/jo701401f. Epub 2007 Sep 12.
6
Additional vinyl ketones and their pyranyl ketones in gonyleptid harvestmen (Arachnida: Opiliones) suggest these metabolites are widespread in this family.戈尼莱普梯德盲蛛（蛛形纲：盲蛛目）中额外的乙烯酮及其吡喃酮表明这些代谢物在这个科中广泛存在。
J Nat Prod. 2013 Sep 27;76(9):1559-64. doi: 10.1021/np4001569. Epub 2013 Aug 26.
7
Sila-Morita-Baylis-Hillman reaction of arylvinyl ketones: overcoming the dimerization problem.芳基乙烯基酮的西拉-森田-贝利斯-希尔曼反应：克服二聚化问题。
Org Lett. 2009 Jan 1;11(1):253-5. doi: 10.1021/ol8026522.
8
Catalytic asymmetric vinylation of ketones.酮的催化不对称乙烯基化反应。
J Am Chem Soc. 2004 Jun 2;126(21):6538-9. doi: 10.1021/ja049206g.
9
Hydrogen-mediated aldol reductive coupling of vinyl ketones catalyzed by rhodium: high syn-selectivity through the effect of tri-2-furylphosphine.铑催化的乙烯基酮的氢介导羟醛还原偶联反应：通过三-2-呋喃基膦的作用实现高顺式选择性
Org Lett. 2006 Feb 2;8(3):519-22. doi: 10.1021/ol052859x.
10
Ruthenium-Lewis acid catalyzed asymmetric Diels-Alder reactions between dienes and alpha,beta-unsaturated ketones.钌-路易斯酸催化二烯与α,β-不饱和酮之间的不对称狄尔斯-阿尔德反应。
Chemistry. 2007;13(12):3354-68. doi: 10.1002/chem.200600851.
引用本文的文献
1
Interplay between Energy and Entropy Mediates Ambimodal Selectivity of Cycloadditions.能量与熵之间的相互作用介导环加成反应的双峰选择性。
J Chem Theory Comput. 2024 Dec 24;20(24):10942-10951. doi: 10.1021/acs.jctc.4c01138. Epub 2024 Dec 6.
2
Computational Design of a Tetrapericyclic Cycloaddition and the Nature of Potential Energy Surfaces with Multiple Bifurcations.四环周环环加成反应的计算设计及具有多个分支的势能面的性质
J Am Chem Soc. 2023 Feb 9;145(7):4221-30. doi: 10.1021/jacs.2c12871.
3
Prediction of the [4 + 2]- and [5 + 4]-cycloaddition reactions in zig-zag carbon nanotubes an ambimodal transition state: density functional theory calculations.锯齿形碳纳米管中[4 + 2]和[5 + 4]环加成反应的预测：双峰过渡态的密度泛函理论计算
RSC Adv. 2020 Mar 17;10(19):11111-11120. doi: 10.1039/c9ra10252c. eCollection 2020 Mar 16.
4
Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode.分叉反应：共享反应模式下能量分布所产生的产物分布
Chem Sci. 2021 Aug 23;12(38):12682-12694. doi: 10.1039/d1sc02826j. eCollection 2021 Oct 6.
5
Mechanisms and Dynamics of Synthetic and Biosynthetic Formation of Delitschiapyrones: Solvent Control of Ambimodal Periselectivity.合成和生物合成 Delitschiapyrones 形成的机制和动力学：溶剂对双模态近选择性的控制。
J Am Chem Soc. 2021 Aug 4;143(30):11734-11740. doi: 10.1021/jacs.1c05293. Epub 2021 Jul 23.
6
Low dimensional representations along intrinsic reaction coordinates and molecular dynamics trajectories using interatomic distance matrices.使用原子间距离矩阵沿本征反应坐标和分子动力学轨迹的低维表示。
Chem Sci. 2019 Sep 18;10(43):9954-9968. doi: 10.1039/c9sc02742d. eCollection 2019 Nov 21.
7
Bond Memory in Dynamically Determined Stereoselectivity.动态确定的立体选择性中的键记忆。
J Am Chem Soc. 2020 Jan 8;142(1):85-88. doi: 10.1021/jacs.9b12227. Epub 2019 Dec 20.
8
Unconventional Reactivity of Ethynylbenziodoxolone Reagents and Thiols: Scope and Mechanism.炔基苯并碘𬭩试剂和硫醇的非常规反应性：范围和机制。
Chemistry. 2020 Feb 21;26(11):2386-2394. doi: 10.1002/chem.201904520. Epub 2020 Jan 22.
9
Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings.四氧化钌氧化饱和环过程中的瞬态和中间体碳正离子
Beilstein J Org Chem. 2019 Jul 11;15:1552-1562. doi: 10.3762/bjoc.15.158. eCollection 2019.
10
Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces.气相、凝聚相及界面处非平衡和非统计动力学的理论与计算研究。
Philos Trans A Math Phys Eng Sci. 2017 Apr 28;375(2092). doi: 10.1098/rsta.2017.0035.
本文引用的文献
1
Entropic intermediates and hidden rate-limiting steps in seemingly concerted cycloadditions. Observation, prediction, and origin of an isotope effect on recrossing.似乎协同环加成中的熵中间体和隐藏的限速步骤。重交叉同位素效应的观察、预测和起源。
J Am Chem Soc. 2012 Feb 1;134(4):1914-7. doi: 10.1021/ja208779k. Epub 2012 Jan 18.
2
Computational study on the reaction pathway of α-bromoacetophenones with hydroxide ion: possible path bifurcation in the addition/substitution mechanism.α-溴代苯乙酮与氢氧根离子反应途径的计算研究：加成/取代机理中可能的分支路径。
J Org Chem. 2011 Oct 21;76(20):8294-9. doi: 10.1021/jo201485y. Epub 2011 Sep 7.
3
Dynamic path bifurcation in the Beckmann reaction: support from kinetic analyses.贝克曼重排反应中的动态路径分岔：来自动力学分析的支持。
J Org Chem. 2011 Jun 3;76(11):4652-60. doi: 10.1021/jo200728t. Epub 2011 May 12.
4
Reaction pathways and possible path bifurcation for the Schmidt reaction.施密特反应的反应途径和可能的路径分岔。
J Am Chem Soc. 2010 Mar 17;132(10):3413-22. doi: 10.1021/ja908899u.
5
Recrossing and dynamic matching effects on selectivity in a Diels-Alder reaction.重交叉和动态匹配效应对 Diels-Alder 反应选择性的影响。
Angew Chem Int Ed Engl. 2009;48(48):9156-9. doi: 10.1002/anie.200903293.
6
Phase space prediction of product branching ratios: canonical competitive nonstatistical model.产物分支比的相空间预测：正则竞争非统计模型。
J Am Chem Soc. 2009 Nov 4;131(43):15754-60. doi: 10.1021/ja904405v.
7
Concerted pyridinolysis of aryl 2,4,6-trinitrophenyl carbonates.芳基 2,4,6-三硝基苯碳酸酯的协同吡啶解。
J Org Chem. 2009 Aug 21;74(16):6374-7. doi: 10.1021/jo901137f.
8
Newtonian kinetic isotope effects. Observation, prediction, and origin of heavy-atom dynamic isotope effects.牛顿动力学同位素效应。重原子动态同位素效应的观测、预测及起源。
J Am Chem Soc. 2009 Jun 24;131(24):8382-3. doi: 10.1021/ja9031083.
9
Control elements in dynamically determined selectivity on a bifurcating surface.分叉表面上动态确定选择性的控制元件。
J Am Chem Soc. 2008 Nov 5;130(44):14544-55. doi: 10.1021/ja802577v. Epub 2008 Oct 11.
10
Ab initio calculations of the potential surface for rearrangement of 2,2,3,3-tetrafluoromethylenecyclopropane to 1-(difluoromethylene)-2,2-difluorocyclopropane.2,2,3,3-四氟亚甲基环丙烷重排为1-(二氟亚甲基)-2,2-二氟环丙烷的势能面的从头算计算。
J Am Chem Soc. 2006 Dec 27;128(51):16676-83. doi: 10.1021/ja065963y.
Zotero 插件