评估远程官能团对氧化还原接力 Heck 反应的影响。
Rate Profiling the Impact of Remote Functional Groups on the Redox-Relay Heck Reaction.
机构信息
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
出版信息
Org Lett. 2021 Apr 2;23(7):2505-2509. doi: 10.1021/acs.orglett.1c00450. Epub 2021 Mar 12.
Abstract
The redox-relay Heck reaction is a powerful method for the construction of enantioenriched quaternary stereocenters remote from existing functional groups. However, there has been little success in the design of site-selective alkene functionalization based on these methods. Herein, we show that experimentally determined rates can be used to train a multivariate linear regression model capable of predicting the rate of a specific relay Heck reaction, allowing for the site-selective functionalization of diene substrates.
摘要
氧化还原接力 Heck 反应是构建手性季碳中心的有力方法，这些季碳中心与现有官能团相隔较远。然而，基于这些方法设计选择性烯烃官能化的方法很少成功。在此，我们表明，实验确定的速率可用于训练多元线性回归模型，该模型能够预测特定的接力 Heck 反应的速率，从而实现二烯底物的选择性官能化。
相似文献
1
Rate Profiling the Impact of Remote Functional Groups on the Redox-Relay Heck Reaction.评估远程官能团对氧化还原接力 Heck 反应的影响。
Org Lett. 2021 Apr 2;23(7):2505-2509. doi: 10.1021/acs.orglett.1c00450. Epub 2021 Mar 12.
2
Mechanism, reactivity, and selectivity in palladium-catalyzed redox-relay Heck arylations of alkenyl alcohols.钯催化的烯丙醇的氧化还原接力 Heck 芳基化反应中的机理、反应性和选择性。
J Am Chem Soc. 2014 Feb 5;136(5):1960-7. doi: 10.1021/ja4109616. Epub 2014 Jan 22.
3
Palladium-Catalyzed Enantioselective Redox-Relay Heck Arylation of 1,1-Disubstituted Homoallylic Alcohols.钯催化的对映选择性氧化还原接力 Heck 芳基化反应 1,1-二取代偕二烯丙基醇。
J Am Chem Soc. 2016 Sep 14;138(36):11461-4. doi: 10.1021/jacs.6b06994. Epub 2016 Sep 1.
4
Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols.研究钯在链烯醇对映选择性氧化还原接力Heck反应中的链行走性质。
J Org Chem. 2014 Dec 19;79(24):11841-50. doi: 10.1021/jo501813d. Epub 2014 Sep 10.
5
Alkenyl carbonyl derivatives in enantioselective redox relay Heck reactions: accessing α,β-unsaturated systems.对映选择性氧化还原接力Heck反应中的烯基羰基衍生物：构建α,β-不饱和体系
J Am Chem Soc. 2015 Jun 17;137(23):7290-3. doi: 10.1021/jacs.5b04289. Epub 2015 Jun 4.
6
Enantioselective Palladium-Catalyzed Alkenylation of Trisubstituted Alkenols To Form Allylic Quaternary Centers.手性钯催化三取代烯丙醇的烯丙基化反应，形成烯丙基季碳中心。
J Am Chem Soc. 2016 Nov 2;138(43):14226-14229. doi: 10.1021/jacs.6b09649. Epub 2016 Oct 25.
7
Enantioselective Heck arylations of acyclic alkenyl alcohols using a redox-relay strategy.使用氧化还原中继策略对非环烯基醇进行对映选择性 Heck 芳基化反应。
Science. 2012 Dec 14;338(6113):1455-8. doi: 10.1126/science.1229208.
8
A Heck-Based Strategy To Generate Anacardic Acids and Related Phenolic Lipids for Isoform-Specific Bioactivity Profiling.基于 Heck 反应的方法用于生成具有特定生物活性构象特征的麻疯树酸和相关酚类脂类化合物。
Org Lett. 2018 Oct 5;20(19):6234-6238. doi: 10.1021/acs.orglett.8b02705. Epub 2018 Sep 25.
9
Palladium-catalyzed oxidative Heck-type alkylation/aryl migration/desulfonylation between alkenes with α-carbonyl alkyl bromides.钯催化的烯烃与α-羰基烷基溴化物之间的氧化 Heck 型烷基化/芳基迁移/脱硫反应。
Org Lett. 2015 Feb 20;17(4):836-9. doi: 10.1021/ol503660a. Epub 2015 Feb 5.
10
Enantioselective Dehydrogenative Heck Arylations of Trisubstituted Alkenes with Indoles to Construct Quaternary Stereocenters.通过三取代烯烃与吲哚的对映选择性脱氢Heck芳基化反应构建季碳立体中心
J Am Chem Soc. 2015 Dec 23;137(50):15668-71. doi: 10.1021/jacs.5b11335. Epub 2015 Dec 10.
本文引用的文献
1
Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction.发展和对在手性接力 Heck 反应中链行走中断的机制探究。
J Am Chem Soc. 2020 Jun 10;142(23):10516-10525. doi: 10.1021/jacs.0c03589. Epub 2020 May 29.
2
Palladium-catalyzed enantioselective alkenylation of alkenylbenzene derivatives.钯催化的烯基苯衍生物的对映选择性烯基化反应。
Chem Sci. 2019 Jun 17;10(30):7246-7250. doi: 10.1039/c9sc02380a. eCollection 2019 Aug 14.
3
Palladium-Catalyzed Enantioselective Relay Heck Arylation of Enelactams: Accessing α,β-Unsaturated δ-Lactams.钯催化的对映选择性接力 Heck 芳基化反应(enelactams)：α,β-不饱和δ-内酰胺的获得。
J Am Chem Soc. 2018 May 30;140(21):6527-6530. doi: 10.1021/jacs.8b02752. Epub 2018 May 16.
4
Predictive and mechanistic multivariate linear regression models for reaction development.反应发展的预测性和机制性多元线性回归模型。
Chem Sci. 2018 Jan 23;9(9):2398-2412. doi: 10.1039/c7sc04679k. eCollection 2018 Mar 7.
5
Pd-Catalyzed Selective Remote Ring Opening of Polysubstituted Cyclopropanols.钯催化的多取代环丙烷醇的选择性远程环开。
Chemistry. 2018 Jun 18;24(34):8553-8557. doi: 10.1002/chem.201802016. Epub 2018 May 22.
6
A unique Pd-catalysed Heck arylation as a remote trigger for cyclopropane selective ring-opening.钯催化 Heck 芳基化作为远程引发环丙烷选择性开环的独特反应。
Nat Commun. 2017 Feb 7;8:14200. doi: 10.1038/ncomms14200.
7
Enantioselective Palladium-Catalyzed Alkenylation of Trisubstituted Alkenols To Form Allylic Quaternary Centers.手性钯催化三取代烯丙醇的烯丙基化反应，形成烯丙基季碳中心。
J Am Chem Soc. 2016 Nov 2;138(43):14226-14229. doi: 10.1021/jacs.6b09649. Epub 2016 Oct 25.
8
Palladium-Catalyzed Long-Range Deconjugative Isomerization of Highly Substituted α,β-Unsaturated Carbonyl Compounds.钯催化的高取代α,β-不饱和羰基化合物的远程去共轭异构化。
J Am Chem Soc. 2016 Aug 17;138(32):10344-50. doi: 10.1021/jacs.6b06390. Epub 2016 Aug 2.
9
Relative reactivity of alkenyl alcohols in the palladium-catalyzed redox-relay Heck reaction.钯催化氧化还原接力Heck反应中烯基醇的相对反应活性
Tetrahedron. 2015 Sep 16;71(37):6513-6518. doi: 10.1016/j.tet.2015.05.020.
10
Alkenyl carbonyl derivatives in enantioselective redox relay Heck reactions: accessing α,β-unsaturated systems.对映选择性氧化还原接力Heck反应中的烯基羰基衍生物：构建α,β-不饱和体系
J Am Chem Soc. 2015 Jun 17;137(23):7290-3. doi: 10.1021/jacs.5b04289. Epub 2015 Jun 4.
Zotero 插件