一种用于分子间烯丙基C-H胺化的催化布朗斯特碱策略。
A catalytic, Brønsted base strategy for intermolecular allylic C-H amination.
作者信息
Reed Sean A, Mazzotti Anthony R, White M Christina
机构信息
Department of Chemistry, Roger Adams Laboratory, University of Illinois, Urbana, Illinois 61801, USA.
出版信息
J Am Chem Soc. 2009 Aug 26;131(33):11701-6. doi: 10.1021/ja903939k.
Abstract
A Brønsted base activation mode for oxidative, Pd(II)/sulfoxide-catalyzed, intermolecular C-H allylic amination is reported. N,N-diisopropylethylamine was found to promote amination of unactivated terminal olefins, forming the corresponding linear allylic amine products with high levels of stereo-, regio-, and chemoselectivity. The predictable and high selectivity of this C-H oxidation method enables late-stage incorporation of nitrogen into advanced synthetic intermediates and natural products.
摘要
报道了一种用于氧化、钯（II）/亚砜催化的分子间C-H烯丙基胺化反应的布朗斯特碱活化模式。发现N，N-二异丙基乙胺可促进未活化末端烯烃的胺化反应，以高立体、区域和化学选择性形成相应的线性烯丙基胺产物。这种C-H氧化方法可预测的高选择性使得能够在后期将氮引入高级合成中间体和天然产物中。
相似文献
1
A catalytic, Brønsted base strategy for intermolecular allylic C-H amination.
J Am Chem Soc. 2009 Aug 26;131(33):11701-6. doi: 10.1021/ja903939k.
2
Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs.
J Am Chem Soc. 2009 Aug 26;131(33):11707-11. doi: 10.1021/ja9054959.
3
Palladium(0)/PAr3 -Catalyzed Intermolecular Amination of C(sp(3) )H Bonds: Synthesis of β-Amino Acids.
Angew Chem Int Ed Engl. 2015 May 26;54(22):6545-9. doi: 10.1002/anie.201502075. Epub 2015 Apr 14.
4
Allylic C-H amination cross-coupling furnishes tertiary amines by electrophilic metal catalysis.
Science. 2022 Apr 15;376(6590):276-283. doi: 10.1126/science.abn8382. Epub 2022 Apr 14.
5
Brønsted base-modulated regioselective pd-catalyzed intramolecular aerobic oxidative amination of alkenes: formation of seven-membered amides and evidence for allylic C-H activation.
Org Lett. 2009 Jun 18;11(12):2707-10. doi: 10.1021/ol900941t.
6
N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.
J Am Chem Soc. 2014 Aug 6;136(31):11176-81. doi: 10.1021/ja506036q. Epub 2014 Jul 24.
7
Palladium-catalyzed aerobic oxidative amination of alkenes: development of intra- and intermolecular aza-Wacker reactions.
Inorg Chem. 2007 Mar 19;46(6):1910-23. doi: 10.1021/ic061997v.
8
Oxidative Pd(II)-catalyzed C-H bond amination to carbazole at ambient temperature.
J Am Chem Soc. 2008 Dec 3;130(48):16184-6. doi: 10.1021/ja806543s.
9
Palladium-catalyzed allylic C-H bond functionalization of olefins.
Top Curr Chem. 2010;292:195-209. doi: 10.1007/128_2009_16.
10
Late-Stage Intermolecular Allylic C-H Amination.
J Am Chem Soc. 2021 Sep 22;143(37):14969-14975. doi: 10.1021/jacs.1c06335. Epub 2021 Sep 13.
引用本文的文献
1
C(sp)H/N(sp) Cross-Coupling Reaction for the Synthesis of Tertiary Arylamines via Fluxional SOX·Pd(II) Catalysis.
J Am Chem Soc. 2025 Aug 28. doi: 10.1021/jacs.5c08883.
2
Allylic C-H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system.
Nat Commun. 2025 Jan 20;16(1):870. doi: 10.1038/s41467-025-56230-0.
3
Halide Perovskite Induces Halogen/Hydrogen Atom Transfer (XAT/HAT) for Allylic C-H Amination.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413012. doi: 10.1002/anie.202413012. Epub 2024 Oct 29.
4
Direct synthesis of branched amines enabled by dual-catalyzed allylic C─H amination of alkenes with amines.
Sci Adv. 2024 Apr 5;10(14):eadn1272. doi: 10.1126/sciadv.adn1272.
5
Synthesis of Borylated Carbocycles by [2 + 2]-Cycloadditions and Photo-Ene Reactions.
J Am Chem Soc. 2024 Apr 10;146(14):10142-10149. doi: 10.1021/jacs.4c01557. Epub 2024 Mar 27.
6
Biocatalytic Transamination of Aldolase-Derived 3-Hydroxy Ketones.
Adv Synth Catal. 2023 May 12;365(9):1485-1495. doi: 10.1002/adsc.202300201. Epub 2023 Apr 26.
7
Asymmetric intermolecular allylic C-H amination of alkenes with aliphatic amines.
Science. 2022 Dec 16;378(6625):1207-1213. doi: 10.1126/science.abq1274. Epub 2022 Dec 15.
8
SulfoxFluor-enabled deoxyazidation of alcohols with NaN.
Nat Commun. 2022 May 18;13(1):2752. doi: 10.1038/s41467-022-30132-x.
9
Intermolecular oxidative amination of unactivated alkenes by dual photoredox and copper catalysis.
Chem Sci. 2020 Dec 8;12(5):1901-1906. doi: 10.1039/d0sc05952h.
10
C-H Activation: Toward Sustainability and Applications.
ACS Cent Sci. 2021 Feb 24;7(2):245-261. doi: 10.1021/acscentsci.0c01413. Epub 2021 Feb 2.
本文引用的文献
1
Oxidative Pd(II)-catalyzed C-H bond amination to carbazole at ambient temperature.
J Am Chem Soc. 2008 Dec 3;130(48):16184-6. doi: 10.1021/ja806543s.
2
Catalytic C-H amination for the preparation of substituted 1,2-diamines.
J Am Chem Soc. 2008 Aug 27;130(34):11248-9. doi: 10.1021/ja803344v. Epub 2008 Aug 5.
3
Enantioselective C-H amination using cationic ruthenium(II)-pybox catalysts.
Angew Chem Int Ed Engl. 2008;47(36):6825-8. doi: 10.1002/anie.200801445.
4
Synthesis of indolines and tetrahydroisoquinolines from arylethylamines by Pd(II)-catalyzed C-H activation reactions.
Angew Chem Int Ed Engl. 2008;47(34):6452-5. doi: 10.1002/anie.200802187.
5
A chiral Lewis acid strategy for enantioselective allylic C-H oxidation.
Angew Chem Int Ed Engl. 2008;47(34):6448-51. doi: 10.1002/anie.200802106.
6
Direct functionalization of nitrogen heterocycles via Rh-catalyzed C-H bond activation.
Acc Chem Res. 2008 Aug;41(8):1013-25. doi: 10.1021/ar800042p. Epub 2008 Jul 11.
7
Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis.
J Am Chem Soc. 2008 Mar 19;130(11):3316-8. doi: 10.1021/ja710206u. Epub 2008 Feb 27.
8
C-H functionalization/C-N bond formation: copper-catalyzed synthesis of benzimidazoles from amidines.
Angew Chem Int Ed Engl. 2008;47(10):1932-4. doi: 10.1002/anie.200705420.
9
Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion.
Nature. 2008 Jan 24;451(7177):417-24. doi: 10.1038/nature06485.
10
Toward a synthetically useful stereoselective C-H amination of hydrocarbons.
J Am Chem Soc. 2008 Jan 9;130(1):343-50. doi: 10.1021/ja076519d. Epub 2007 Dec 12.
Zotero 插件