烯丙基化反应：烯烃的形式 σ-键复分解反应。
Dealkenylative Alkenylation: Formal σ-Bond Metathesis of Olefins.
机构信息
Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, CA, 90095-1569, USA.
出版信息
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17565-17571. doi: 10.1002/anie.202005267. Epub 2020 Aug 28.
Abstract
The dealkenylative alkenylation of alkene C(sp )-C(sp ) bonds has been an unexplored area for C-C bond formation. Herein 64 examples of β-alkylated styrene derivatives, synthesized through the reactions of readily accessible feedstock olefins with β-nitrostyrenes by ozone/Fe -mediated radical substitutions, are reported. These reactions proceed with good efficiencies and high stereoselectivities under mild reaction conditions and tolerate an array of functional groups. Also demonstrated is the applicability of the strategy through several synthetic transformations of the products, as well as the syntheses of the natural product iso-moracin and the drug (E)-metanicotine.
摘要
烯丙基 C(sp)-C(sp)键的去烯丙基烯基化反应是 C-C 键形成的一个未探索的领域。在此，通过臭氧/Fe 介导的自由基取代反应，用易得的原料烯烃与β-硝基苯乙烯反应，合成了 64 个β-烷基化苯乙烯衍生物。这些反应在温和的反应条件下以良好的效率和高立体选择性进行，并且可以耐受多种官能团。还通过对产物的几种合成转化以及天然产物异吗红宁和药物(E)-烟碱的合成，证明了该策略的适用性。
相似文献
1
Dealkenylative Alkenylation: Formal σ-Bond Metathesis of Olefins.烯丙基化反应：烯烃的形式 σ-键复分解反应。
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17565-17571. doi: 10.1002/anie.202005267. Epub 2020 Aug 28.
2
Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.通过钯催化的烯基化-羰基烯化协同作用高效选择性合成二取代、三取代和四取代烯烃的最新进展。
Acc Chem Res. 2008 Nov 18;41(11):1474-85. doi: 10.1021/ar800038e.
3
Palladium-catalyzed hydroalkylation of styrenes with organozinc reagents to form carbon-carbon sp3-sp3 bonds under oxidative conditions.钯催化的苯乙烯与有机锌试剂的氢烷基化反应在氧化条件下形成碳-碳 sp3-sp3 键。
J Am Chem Soc. 2009 Dec 23;131(50):18042-3. doi: 10.1021/ja908545b.
4
Dealkenylative Thiylation of C(sp)-C(sp) Bonds.C(sp)-C(sp) 键的去烯基硫醚化反应。
Org Lett. 2019 Nov 1;21(21):8592-8597. doi: 10.1021/acs.orglett.9b03186. Epub 2019 Oct 1.
5
Dehydrogenative Pd and Ni Catalysis for Total Synthesis.脱氢 Pd 和 Ni 催化全合成。
Acc Chem Res. 2021 Mar 2;54(5):1118-1130. doi: 10.1021/acs.accounts.0c00787. Epub 2021 Feb 16.
6
Palladium-catalyzed unactivated β-methylene C(sp(3))-H bond alkenylation of aliphatic amides and its application in a sequential C(sp(3))-H/C(sp(2))-H bond alkenylation.钯催化脂肪族酰胺的未活化β-亚甲基C(sp(3))-H键烯基化反应及其在连续C(sp(3))-H/C(sp(2))-H键烯基化反应中的应用
Org Biomol Chem. 2015 Jan 21;13(3):697-701. doi: 10.1039/c4ob02389g.
7
Metathesis reactions in total synthesis.全合成中的复分解反应。
Angew Chem Int Ed Engl. 2005 Jul 18;44(29):4490-527. doi: 10.1002/anie.200500369.
8
Organocatalytic asymmetric Michael addition of α-alkylidene succinimides to nitrostyrenes.α-亚烷基琥珀酰亚胺与硝基苯乙烯的有机催化不对称迈克尔加成反应。
Org Biomol Chem. 2016 Jul 14;14(26):6337-45. doi: 10.1039/c6ob00711b. Epub 2016 Jun 8.
9
A general model for selectivity in olefin cross metathesis.烯烃交叉复分解反应选择性的通用模型。
J Am Chem Soc. 2003 Sep 17;125(37):11360-70. doi: 10.1021/ja0214882.
10
CuH-Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition.CuH 催化的烯烃官能化：从氨氢化反应到羰基加成反应。
Acc Chem Res. 2020 Jun 16;53(6):1229-1243. doi: 10.1021/acs.accounts.0c00164. Epub 2020 May 13.
引用本文的文献
1
Redox-neutral photocatalytic hydrodealkenylation of aryl olefins.芳基烯烃的氧化还原中性光催化氢脱烯基化反应
Nat Commun. 2025 Jul 1;16(1):5553. doi: 10.1038/s41467-025-60229-y.
2
Hydrodealkenylative Cleavage of C(sp)-C(sp) Bonds: Preparation of (1, 3)-3-Methylcyclohexan-1-ol.C(sp)-C(sp)键的氢脱烯基裂解反应：(1, 3)-3-甲基环己醇的制备
Organic Synth. 2024;101:488-507. doi: 10.15227/orgsyn.101.0488. Epub 2024 Dec 4.
3
Synthesis through C(sp)-C(sp) Bond Scission in Alkenes and Ketones.通过烯烃和酮中C(sp)-C(sp)键断裂进行的合成。
Acc Chem Res. 2025 May 6;58(9):1547-1561. doi: 10.1021/acs.accounts.5c00156. Epub 2025 Apr 15.
4
Hydrodealkenylative C(sp)-C(sp) Bond Fragmentation Using Isayama-Mukaiyama Peroxidation.使用Isayama-Mukaiyama过氧化反应的氢脱烯基化C(sp)-C(sp)键断裂反应
J Am Chem Soc. 2025 Apr 23;147(16):13531-13544. doi: 10.1021/jacs.5c00540. Epub 2025 Apr 15.
5
Halodealkenylation: Ozonolysis and Catalytic Fe with Vitamin C Convert C(sp)-C(sp) Bonds to C(sp)-Halide Bonds.卤代烯基化反应：臭氧分解以及铁与维生素C催化将C(sp)-C(sp)键转化为C(sp)-卤化物键。
Org Lett. 2024 Dec 20;26(50):10921-10927. doi: 10.1021/acs.orglett.4c04084. Epub 2024 Dec 9.
6
Dealkenylative Functionalizations: Conversion of Alkene C(sp)-C(sp) Bonds into C(sp)-X Bonds via Redox-Based Radical Processes.脱烯基官能团化反应：通过基于氧化还原的自由基过程将烯烃C(sp)-C(sp)键转化为C(sp)-X键
Synthesis (Stuttg). 2024 Jan;56(1):71-86. doi: 10.1055/a-2044-4571. Epub 2023 Apr 12.
7
When all C-C breaks LO-Ose.当所有的C-C键断裂时，就失去了“LO-Ose”（此句可能在特定语境下有特定含义，单纯从字面看较奇特） 。
Trends Chem. 2023 Mar;5(3):174-200. doi: 10.1016/j.trechm.2023.01.001. Epub 2023 Feb 14.
8
Dealkenylative Alkynylation Using Catalytic Fe and Vitamin C.使用催化铁和维生素 C 的去烯丙基炔基化反应。
J Am Chem Soc. 2022 Aug 17;144(32):14828-14837. doi: 10.1021/jacs.2c05980. Epub 2022 Aug 4.
9
A donor-acceptor complex enables the synthesis of -olefins from alcohols, amines and carboxylic acids.供体-受体络合物可实现由醇、胺和羧酸合成烯烃。
Chem Sci. 2021 Apr 5;12(19):6684-6690. doi: 10.1039/d1sc01024g.
本文引用的文献
1
Lewis acid-catalyzed carbonyl-olefin metathesis.路易斯酸催化的羰基-烯烃复分解反应
Trends Chem. 2019 May;1(2):272-273. doi: 10.1016/j.trechm.2019.02.011. Epub 2019 Mar 15.
2
Oxodealkenylative Cleavage of Alkene C(sp )-C(sp ) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials.烯烃C(sp³)-C(sp³)键的氧化脱烯基裂解：一种将羰基引入手性源材料的实用方法。
Angew Chem Int Ed Engl. 2020 Jan 13;59(3):1211-1215. doi: 10.1002/anie.201913201. Epub 2019 Dec 2.
3
Transition-Metal-Catalyzed Alkyl Heck-Type Reactions.过渡金属催化的烷基Heck型反应。
Synthesis (Stuttg). 2019;51(5):985-1005. doi: 10.1055/s-0037-1611659. Epub 2019 Feb 7.
4
Dealkenylative Thiylation of C(sp)-C(sp) Bonds.C(sp)-C(sp) 键的去烯基硫醚化反应。
Org Lett. 2019 Nov 1;21(21):8592-8597. doi: 10.1021/acs.orglett.9b03186. Epub 2019 Oct 1.
5
Triphenylphosphonium Analogues of Betulin and Betulinic Acid with Biological Activity: A Comprehensive Review.三苯基膦类似物的白桦脂醇和白桦脂酸与生物活性：全面审查。
J Nat Prod. 2019 Jun 28;82(6):1719-1730. doi: 10.1021/acs.jnatprod.8b00830. Epub 2019 May 29.
6
Hydrodealkenylative C(sp)-C(sp) bond fragmentation.氢脱烯丙基化 C(sp)-C(sp)键断裂
Science. 2019 May 17;364(6441):681-685. doi: 10.1126/science.aaw4212.
7
A Systematic Cheminformatics Analysis of Functional Groups Occurring in Natural Products.天然产物中功能团的系统化学信息学分析。
J Nat Prod. 2019 May 24;82(5):1258-1263. doi: 10.1021/acs.jnatprod.8b01022. Epub 2019 Apr 1.
8
Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation.通过光激发态金属催化实现钯(0)的氧化加成：实验与计算
Angew Chem Int Ed Engl. 2019 Mar 11;58(11):3412-3416. doi: 10.1002/anie.201811439. Epub 2019 Jan 9.
9
Alkenylation of unactivated alkyl bromides through visible light photocatalysis.通过可见光光催化实现非活化烷基溴的烯丙基化反应。
Chem Commun (Camb). 2018 Dec 18;55(1):107-110. doi: 10.1039/c8cc08362b.
10
Carvone-Derived P-Stereogenic Phosphines: Design, Synthesis, and Use in Allene-Imine [3 + 2] Annulation.香芹酮衍生的P-手性膦：设计、合成及其在丙二烯-亚胺[3 + 2]环化反应中的应用
ACS Catal. 2018 Jun 1;8(6):5188-5192. doi: 10.1021/acscatal.8b01081. Epub 2018 May 4.
Zotero 插件