作为动力学隐藏过渡态探针的能量读出
Energy Read-out as a Probe of Kinetically Hidden Transition States.
作者信息
Alvi Scheherzad, Singleton Daniel A
机构信息
Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012, United States.
出版信息
Org Lett. 2021 Mar 19;23(6):2174-2177. doi: 10.1021/acs.orglett.1c00324. Epub 2021 Mar 2.
Abstract
The initial energy in a reactive intermediate is derived from the transition state the intermediate but can affect selectivity the intermediate. In this way an observable selectivity can report on a prior, kinetically hidden mechanistic step. This new type of mechanistic probe is demonstrated here for the oxidation of 1-methylcyclobutanol by phthaloyl peroxide/BuNBr, and it supports a hypobromite chain mechanism in place of the previously proposed hydrogen atom transfer mechanism.
摘要
反应中间体的初始能量源自过渡态，该中间体虽能影响选择性，但也能影响中间体。通过这种方式，可观测到的选择性能够反映出之前动力学上隐藏的机理步骤。本文展示了这种新型机理探针用于邻苯二甲酰过氧化物/丁基溴化铵对1 - 甲基环丁醇的氧化反应，它支持次溴酸盐链式机理，而非先前提出的氢原子转移机理。
相似文献
1
Energy Read-out as a Probe of Kinetically Hidden Transition States.作为动力学隐藏过渡态探针的能量读出
Org Lett. 2021 Mar 19;23(6):2174-2177. doi: 10.1021/acs.orglett.1c00324. Epub 2021 Mar 2.
2
Mechanistic molecular motion of transition-metal mediated β-hydrogen transfer: quasiclassical trajectories reveal dynamically ballistic, dynamically unrelaxed, two step, and concerted mechanisms.过渡金属介导的β-氢转移的分子机理运动：准经典轨迹揭示了动态弹道、动态非弛豫、两步和协同机制。
Dalton Trans. 2020 Jun 16;49(23):7747-7757. doi: 10.1039/d0dt01687j.
3
Ab Initio/Transition-State Theory Study of the Reactions of ĊH Species of Relevance to 1,3-Pentadiene, Part I: Potential Energy Surfaces, Thermochemistry, and High-Pressure Limiting Rate Constants.从头算/过渡态理论研究与 1,3-戊二烯有关的 ĊH 物种的反应，第一部分：势能面、热化学和高压限制速率常数。
J Phys Chem A. 2019 Oct 24;123(42):9019-9052. doi: 10.1021/acs.jpca.9b06628. Epub 2019 Oct 15.
4
Transition from hydrogen atom to hydride abstraction by Mn4O4(O2PPh2)6 versus [Mn4O4(O2PPh2)6]+: O-H bond dissociation energies and the formation of Mn4O3(OH)(O2PPh2)6.通过Mn4O4(O2PPh2)6与[Mn4O4(O2PPh2)6]+从氢原子到氢化物提取的转变：O-H键解离能与Mn4O3(OH)(O2PPh2)6的形成
Inorg Chem. 2003 May 5;42(9):2849-58. doi: 10.1021/ic025977e.
5
Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.从反应相的角度对化学反应机制进行计算分析：隐藏的中间产物和隐藏的过渡态。
Acc Chem Res. 2010 May 18;43(5):591-601. doi: 10.1021/ar900013p.
6
Chemiluminescence from the oxidation of urea and ammonia with hypobromite and N-bromosuccinimide.尿素和氨与次溴酸盐及N-溴代琥珀酰亚胺氧化反应产生的化学发光。
Talanta. 2004 Oct 8;64(2):283-9. doi: 10.1016/j.talanta.2004.02.031.
7
Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.担载 Pt 团簇上 CH4-O2 催化反应中化学吸附氧原子的反应性及其催化后果。
J Am Chem Soc. 2011 Oct 12;133(40):15958-78. doi: 10.1021/ja202411v. Epub 2011 Sep 15.
8
On the mechanisms of oxidation of organic sulfides by H2O2 in aqueous solutions.关于水溶液中过氧化氢对有机硫化物的氧化机理
J Am Chem Soc. 2004 Jan 28;126(3):900-8. doi: 10.1021/ja036762m.
9
On the mechanism of the copper-catalyzed cyclopropanation reaction.关于铜催化环丙烷化反应的机理
Chemistry. 2002 Jan 4;8(1):177-84. doi: 10.1002/1521-3765(20020104)8:1<177::aid-chem177>3.0.co;2-h.
10
Kinetic isotope effects as probes of the mechanism of galactose oxidase.动力学同位素效应作为半乳糖氧化酶作用机制的探针
Biochemistry. 1998 Jun 9;37(23):8426-36. doi: 10.1021/bi980328t.
引用本文的文献
1
Predicting Collision-Induced-Dissociation Tandem Mass Spectra (CID-MS/MS) Using Ab Initio Molecular Dynamics.使用从头算分子动力学预测碰撞诱导解离串联质谱（CID-MS/MS）。
J Chem Inf Model. 2024 Oct 14;64(19):7470-7487. doi: 10.1021/acs.jcim.4c00760. Epub 2024 Sep 27.
2
Revealing the nature of covalently tethered distonic radical anions in the generation of heteroatom-centered radicals: evidence for the polarity-matching PCET pathway.揭示在以杂原子为中心的自由基生成过程中共价连接的双自由基阴离子的本质：极性匹配的质子耦合电子转移途径的证据。
Chem Sci. 2024 Jun 28;15(31):12398-12409. doi: 10.1039/d4sc02602k. eCollection 2024 Aug 7.
本文引用的文献
1
Catalytic generation of alkoxy radicals from unfunctionalized alcohols.从未官能化的醇类催化生成烷氧基自由基。
Chem Sci. 2020 Sep 21;11(41):11124-11141. doi: 10.1039/d0sc04542j. eCollection 2020 Nov 7.
2
Remote Nickel-Catalyzed Cross-Coupling Arylation via Proton-Coupled Electron Transfer-Enabled C-C Bond Cleavage.通过质子耦合电子转移促进的 C-C 键断裂实现的远程镍催化交叉偶联芳基化反应。
J Am Chem Soc. 2020 Feb 19;142(7):3532-3539. doi: 10.1021/jacs.9b12490. Epub 2020 Feb 4.
3
δ-C-H Mono- and Dihalogenation of Alcohols.醇的δ-C-H单卤化和二卤化
J Am Chem Soc. 2020 Feb 12;142(6):2766-2770. doi: 10.1021/jacs.9b13171. Epub 2020 Jan 30.
4
Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals.锰催化环烷醇通过烷氧基自由基进行的电化学解构氯化反应
Org Lett. 2019 Nov 15;21(22):9241-9246. doi: 10.1021/acs.orglett.9b03652. Epub 2019 Nov 5.
5
A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions.一种用于光驱动、非平衡异构化的氧化还原策略及其在催化 C-C 键断裂反应中的应用。
J Am Chem Soc. 2019 Jan 30;141(4):1457-1462. doi: 10.1021/jacs.8b12552. Epub 2019 Jan 15.
6
Cerium-Catalyzed Formal Cycloaddition of Cycloalkanols with Alkenes through Dual Photoexcitation.铈催化环烷醇与烯烃通过双光激发进行形式上的环加成反应。
J Am Chem Soc. 2018 Oct 24;140(42):13580-13585. doi: 10.1021/jacs.8b08781. Epub 2018 Oct 9.
7
Visible light-promoted ring-opening functionalization of unstrained cycloalkanols inert C-C bond scission.可见光促进的无张力环烷醇的开环官能团化及惰性C-C键断裂
Chem Sci. 2018 Jun 11;9(26):5805-5809. doi: 10.1039/c8sc01763h. eCollection 2018 Jul 14.
8
Sulfonamide-Directed Chemo- and Site-Selective Oxidative Halogenation/Amination Using Halogenating Reagents Generated in Situ from Cyclic Diacyl Peroxides.使用环状二酰基过氧化物原位生成的卤化试剂进行磺胺定向的化学和位点选择性氧化卤化/氨基化反应。
J Org Chem. 2018 Mar 16;83(6):3305-3315. doi: 10.1021/acs.joc.8b00243. Epub 2018 Mar 2.
9
Visible-Light-Enhanced Ring Opening of Cycloalkanols Enabled by Brønsted Base-Tethered Acyloxy Radical Induced Hydrogen Atom Transfer-Electron Transfer.布朗斯特碱稳定的酰氧基自由基诱导氢原子转移-电子转移促进的环烷醇的可见光促进开环反应。
Org Lett. 2018 Feb 16;20(4):1228-1231. doi: 10.1021/acs.orglett.8b00161. Epub 2018 Feb 8.
10
Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity.通过能量依赖的反应选择性，实现对反应中间体在溶液中的能量进行标记和测定。
Nat Chem. 2018 Feb;10(2):237-241. doi: 10.1038/nchem.2907. Epub 2018 Jan 1.
Zotero 插件