NHC 基催化剂促进的芳基取代烯烃的高效硼铜加成反应。对映选择性 Cu 催化的硼氢化反应。
Efficient boron-copper additions to aryl-substituted alkenes promoted by NHC-based catalysts. enantioselective Cu-catalyzed hydroboration reactions.
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
出版信息
J Am Chem Soc. 2009 Mar 11;131(9):3160-1. doi: 10.1021/ja809382c.
Abstract
A Cu-catalyzed method for efficient boron-copper addition processes involving acyclic and cyclic disubstituted aryl olefins are reported. Reactions are promoted with 0.5-5 mol % of a readily available N-heterocyclic carbene (NHC) complex; the presence of MeOH promotes in situ protonation of the C-Cu bond and leads to efficient catalyst turnover, constituting a net Cu-catalyzed hydroboration process. Reactions proceed in >98:<2 site selectivity and furnish secondary organoborane isomers that complement those obtained through reactions of boron-hydride reagents or by Rh- or Ir-catalyzed hydroborations (benzylic secondary C-B bonds). Initial observations regarding processes catalyzed by chiral NHC complexes, delivering products in up to 99:1 enantiomeric ratio, are disclosed.
摘要
报道了一种涉及非环和环取代的芳基烯烃的硼铜加成过程的高效铜催化方法。反应在 0.5-5 mol%的易得的 N-杂环卡宾（NHC）配合物的促进下进行；甲醇的存在促进了 C-Cu 键的原位质子化，并导致有效的催化剂周转，构成了净铜催化的硼氢化过程。反应具有>98:<2 的位选择性，并提供了补充通过硼氢化物试剂或 Rh 或 Ir 催化的硼氢化反应获得的那些的次级有机硼烷异构体（苄基次级 C-B 键）。披露了关于手性 NHC 配合物催化的过程的初步观察结果，这些过程以高达 99:1 的对映体比例提供产物。
相似文献
1
Efficient boron-copper additions to aryl-substituted alkenes promoted by NHC-based catalysts. enantioselective Cu-catalyzed hydroboration reactions.NHC 基催化剂促进的芳基取代烯烃的高效硼铜加成反应。对映选择性 Cu 催化的硼氢化反应。
J Am Chem Soc. 2009 Mar 11;131(9):3160-1. doi: 10.1021/ja809382c.
2
N-Heterocyclic Carbene-Copper-Catalyzed Group-, Site-, and Enantioselective Allylic Substitution with a Readily Accessible Propargyl(pinacolato)boron Reagent: Utility in Stereoselective Synthesis and Mechanistic Attributes.N-杂环卡宾-铜催化的具有易得丙炔基（频哪醇）硼试剂的基团、位点和对映选择性烯丙基取代反应：在立体选择性合成中的应用和反应机理。
J Am Chem Soc. 2015 Jul 22;137(28):8948-64. doi: 10.1021/jacs.5b05805. Epub 2015 Jul 14.
3
A broadly applicable NHC-Cu-catalyzed approach for efficient, site-, and enantioselective coupling of readily accessible (pinacolato)alkenylboron compounds to allylic phosphates and applications to natural product synthesis.一种广泛适用的 NHC-Cu 催化方法，用于高效、位点和对映选择性地偶联易得的（频哪醇基）烯基硼化合物与烯丙基磷酸酯，并应用于天然产物合成。
J Am Chem Soc. 2014 Feb 5;136(5):2149-61. doi: 10.1021/ja4126565. Epub 2014 Jan 28.
4
Enantioselective synthesis of allylboronates bearing a tertiary or quaternary B-substituted stereogenic carbon by NHC-Cu-catalyzed substitution reactions.手性 NHC-Cu 催化取代反应合成含叔碳或季碳手性取代基的烯丙基硼酸酯
J Am Chem Soc. 2010 Aug 11;132(31):10634-7. doi: 10.1021/ja104254d.
5
Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.手性氮杂环卡宾铜配合物催化的环状和非环状不饱和羰基化合物的对映选择性共轭硅烷加成反应。
J Am Chem Soc. 2010 Mar 10;132(9):2898-900. doi: 10.1021/ja910989n.
6
Monodentate non-C(2)-symmetric chiral N-heterocyclic carbene complexes for enantioselective synthesis. Cu-catalyzed conjugate additions of aryl- and alkenylsilylfluorides to cyclic enones.用于对映选择性合成的单齿非C(2)对称手性N-杂环卡宾配合物。铜催化芳基和烯基甲硅烷基氟化物对环状烯酮的共轭加成反应。
J Org Chem. 2009 Jun 19;74(12):4455-62. doi: 10.1021/jo900589x.
7
Versatile Homoallylic Boronates by Chemo-, S 2'-, Diastereo- and Enantioselective Catalytic Sequence of Cu-H Addition to Vinyl-B(pin)/Allylic Substitution.通过铜-氢加成到乙烯基-B(pin)/烯丙基取代的化学、S 2'、非对映选择性和对映选择性催化序列实现多功能偕丙基硼酸酯。
Angew Chem Int Ed Engl. 2017 Jan 16;56(3):821-826. doi: 10.1002/anie.201611444. Epub 2016 Dec 20.
8
Enantioselective synthesis of boron-substituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters.手性 NHC-Cu 催化硼酸盐与不饱和羧酸酯、酮或硫酯的共轭加成反应合成硼取代的季碳中心
J Am Chem Soc. 2010 Aug 11;132(31):10630-3. doi: 10.1021/ja104777u.
9
Sulfonate N-Heterocyclic Carbene-Copper Complexes: Uniquely Effective Catalysts for Enantioselective Synthesis of C-C, C-B, C-H, and C-Si Bonds.磺酸酯 N-杂环卡宾-铜配合物：手性合成 C-C、C-B、C-H 和 C-Si 键的高效独特催化剂。
Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21304-21359. doi: 10.1002/anie.202003755. Epub 2020 Aug 26.
10
Enantioselective synthesis of alkyne-substituted quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution reactions with (i-Bu)2(alkynyl)aluminum reagents.手性 N-杂环卡宾铜催化（i-Bu）2（炔基）铝试剂与烯丙基取代反应对炔基取代的季碳手性中心的对映选择性合成。
J Am Chem Soc. 2011 Apr 6;133(13):4778-81. doi: 10.1021/ja2010829. Epub 2011 Mar 8.
引用本文的文献
1
Development of New Indole-Based -Heterocyclic Carbene Copper Complexes and Their Applications in Catalysis.新型吲哚基-杂环卡宾铜配合物的开发及其在催化中的应用。
J Org Chem. 2025 Jun 6;90(22):7236-7245. doi: 10.1021/acs.joc.5c00248. Epub 2025 May 28.
2
Synthesis of α-substituted cyclic boronates titanium-catalyzed cyclization of vinyl boronates with dihaloalkanes.α-取代环硼酸酯的合成：乙烯基硼酸酯与二卤代烷的钛催化环化反应。
Chem Sci. 2025 Mar 12;16(15):6515-6521. doi: 10.1039/d5sc01132a. eCollection 2025 Apr 9.
3
The current utility and future potential of multiborylated alkanes.多硼化烷烃的当前用途及未来潜力。
Nat Rev Chem. 2024 Oct;8(10):741-761. doi: 10.1038/s41570-024-00650-x. Epub 2024 Sep 26.
4
Asymmetric synthesis of chiral (thio)chromanes and exploration on their structure-activity relationship in macrophages.手性（硫）色满的不对称合成及其在巨噬细胞中的构效关系探索。
RSC Adv. 2023 Oct 17;13(43):30391-30400. doi: 10.1039/d3ra06428j. eCollection 2023 Oct 11.
5
Copper-Catalyzed Borylation of Styrenes by 1,8-Diaminonaphthalene-Protected Diboronic Acid.铜催化的 1,8-二氨基萘保护的二硼酸对苯乙烯的硼化反应。
Org Lett. 2023 Mar 31;25(12):2093-2097. doi: 10.1021/acs.orglett.3c00451. Epub 2023 Mar 22.
6
Design and characterization of an urea-bridged PMO supporting Cu(II) nanoparticles as highly efficient heterogeneous catalyst for synthesis of tetrazole derivatives.设计和表征一种尿素桥联的 PMO 支撑的 Cu(II)纳米粒子作为高效的非均相催化剂，用于合成四唑衍生物。
Sci Rep. 2022 Oct 28;12(1):18139. doi: 10.1038/s41598-022-22905-7.
7
Asymmetric synthesis of flavanols via Cu-catalyzed kinetic resolution of chromenes and their anti-inflammatory activity.通过铜催化色烯的动力学拆分实现黄烷醇的不对称合成及其抗炎活性。
Sci Adv. 2022 Jun 3;8(22):eabm9603. doi: 10.1126/sciadv.abm9603.
8
Stereocontrolled Pericyclic and Radical Cycloaddition Reactions of Readily Accessible Chiral Alkenyl Diazaborolidines.易于获得的手性烯基重氮硼烷的立体控制周环反应和自由基环加成反应
Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202205454. doi: 10.1002/anie.202205454. Epub 2022 Jun 8.
9
Tetrazol-Cu(i) immobilized on nickel ferrite catalyzed green synthesis of indenopyridopyrimidine derivatives in aqueous media.固定在铁酸镍上的四氮唑 - 铜（I）催化在水介质中绿色合成茚并吡啶嘧啶衍生物。
RSC Adv. 2021 Sep 22;11(50):31377-31384. doi: 10.1039/d1ra05889d. eCollection 2021 Sep 21.
10
Palladium-catalyzed hydroboration reaction of unactivated alkynes with bis (pinacolato) diboron in water.钯催化未活化炔烃与双（频哪醇）二硼在水中的硼氢化反应。
RSC Adv. 2022 Mar 29;12(16):9815-9820. doi: 10.1039/d1ra09136k. eCollection 2022 Mar 25.
本文引用的文献
1
Copper-catalyzed enantioselective substitution of allylic carbonates with diboron: an efficient route to optically active alpha-chiral allylboronates.铜催化碳酸烯丙酯与二硼的对映选择性取代反应：一种合成光学活性α-手性烯丙基硼酸酯的有效方法。
J Am Chem Soc. 2007 Dec 5;129(48):14856-7. doi: 10.1021/ja076634o. Epub 2007 Nov 8.
2
New N-heterocyclic carbene ligand and its application in asymmetric nickel-catalyzed aldehyde/alkyne reductive couplings.新型氮杂环卡宾配体及其在不对称镍催化的醛/炔还原偶联反应中的应用
J Am Chem Soc. 2007 Aug 8;129(31):9568-9. doi: 10.1021/ja072992f. Epub 2007 Jul 12.
3
All-carbon quaternary stereogenic centers by enantioselective cu-catalyzed conjugate additions promoted by a chiral N-heterocyclic carbene.通过手性N-杂环卡宾促进的对映选择性铜催化共轭加成反应构建全碳季碳立体中心。
Angew Chem Int Ed Engl. 2007;46(7):1097-100. doi: 10.1002/anie.200604511.
4
A valuable, inexpensive Cui/n-heterocyclic carbene catalyst for the selective diboration of styrene.一种用于苯乙烯选择性双硼化反应的有价值且廉价的铜/氮杂环卡宾催化剂。
Chemistry. 2007;13(9):2614-21. doi: 10.1002/chem.200601146.
5
Copper-catalyzed beta-Boration of alpha,beta-unsaturated carbonyl compounds: rate acceleration by alcohol additives.铜催化的α,β-不饱和羰基化合物的β-硼化反应：醇添加剂对反应速率的加速作用
Org Lett. 2006 Oct 12;8(21):4887-9. doi: 10.1021/ol061955a.
6
Efficient homogeneous catalysis in the reduction of CO2 to CO.将二氧化碳高效均相催化还原为一氧化碳。
J Am Chem Soc. 2005 Dec 14;127(49):17196-7. doi: 10.1021/ja0566679.
7
A readily available chiral Ag-based N-heterocyclic carbene complex for use in efficient and highly enantioselective Ru-catalyzed olefin metathesis and Cu-catalyzed allylic alkylation reactions.一种易于获得的手性银基氮杂环卡宾配合物，用于高效且高对映选择性的钌催化烯烃复分解反应和铜催化烯丙基烷基化反应。
J Am Chem Soc. 2005 May 11;127(18):6877-82. doi: 10.1021/ja050179j.
8
Bidentate NHC-based chiral ligands for efficient Cu-catalyzed enantioselective allylic alkylations: structure and activity of an air-stable chiral Cu complex.用于高效铜催化对映选择性烯丙基烷基化反应的双齿NHC基手性配体：一种空气稳定的手性铜配合物的结构与活性
J Am Chem Soc. 2004 Sep 15;126(36):11130-1. doi: 10.1021/ja046245j.
9
Catalytic asymmetric hydroboration/amination and alkylamination with rhodium complexes of 1,1'-(2-diarylphosphino-1-naphthyl)isoquinoline.1,1'-（2-二芳基膦基-1-萘基）异喹啉铑配合物催化的不对称硼氢化/胺化及烷基胺化反应
Chemistry. 2000 May 15;6(10):1840-6. doi: 10.1002/(sici)1521-3765(20000515)6:10<1840::aid-chem1840>3.0.co;2-6.
Zotero 插件