通过 Ti(ii)/Ti(iv) 氧化还原催化将叠氮化物向炔烃的氧化亚氮转移：吡咯的形式[2+2+1]合成。
Oxidative nitrene transfer from azides to alkynes via Ti(ii)/Ti(iv) redox catalysis: formal [2+2+1] synthesis of pyrroles.
机构信息
Department of Chemistry, University of Minnesota - Twin Cities, Minneapolis, MN 55455, USA.
出版信息
Chem Commun (Camb). 2018 Jun 19;54(50):6891-6894. doi: 10.1039/c8cc02623h.
Abstract
Catalytic oxidative nitrene transfer from azides with the early transition metals is rare, and has not been observed without the support of redox noninnocent spectator ligands. Here, we report the formal [2+2+1] coupling of azides and alkynes via TiII/TiIV redox catalysis from simple Ti halide imido precatalysts. These reactions yield polysubstituted N-alkyl pyrroles, including N-benzyl protected pyrroles and rare examples of very electron rich pentaalkyl pyrroles. Mechanistic analysis reveals that [2+2+1] reactions with bulky azides have different mechanistic features from previously-reported reactions using azobenzene as a nitrene source.
摘要
氮烯从叠氮化物向早期过渡金属的催化氧化转移很少见，并且如果没有氧化还原非中性 spectator 配体的支持，这种转移就不会发生。在这里，我们报告了通过简单的 Ti 卤化物亚胺前催化剂从 TiII/TiIV 氧化还原催化作用下，叠氮化物和炔烃的形式[2+2+1]偶联。这些反应生成了多取代的 N-烷基吡咯，包括 N-苄基保护的吡咯和非常富电子的五烷基吡咯的罕见实例。机理分析表明，具有大体积叠氮化物的[2+2+1]反应具有与以前报道的使用偶氮苯作为氮烯源的反应不同的机理特征。
相似文献
1
Oxidative nitrene transfer from azides to alkynes via Ti(ii)/Ti(iv) redox catalysis: formal [2+2+1] synthesis of pyrroles.通过 Ti(ii)/Ti(iv) 氧化还原催化将叠氮化物向炔烃的氧化亚氮转移：吡咯的形式[2+2+1]合成。
Chem Commun (Camb). 2018 Jun 19;54(50):6891-6894. doi: 10.1039/c8cc02623h.
2
Ti-Catalyzed and -Mediated Oxidative Amination Reactions.钛催化和介导的氧化氨化反应。
Acc Chem Res. 2021 Sep 7;54(17):3476-3490. doi: 10.1021/acs.accounts.1c00368. Epub 2021 Aug 22.
3
Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via Ti(II)/Ti(IV) redox catalysis.通过 Ti(II)/Ti(IV) 氧化还原催化，炔烃和重氮化合物催化形式[2+2+1]合成吡咯。
Nat Chem. 2016 Jan;8(1):63-8. doi: 10.1038/nchem.2386. Epub 2015 Nov 2.
4
Mechanism of Ti-Catalyzed Oxidative Nitrene Transfer in [2 + 2 + 1] Pyrrole Synthesis from Alkynes and Azobenzene.钛催化炔烃和偶氮苯的[2 + 2 + 1]吡咯合成中环化氧化氮转移反应的机理。
J Am Chem Soc. 2018 Jun 13;140(23):7267-7281. doi: 10.1021/jacs.8b03546. Epub 2018 May 31.
5
Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides.通过钛催化二氮烯向异腈的氮烯转移合成碳二亚胺。
ACS Catal. 2019 Dec 6;9(12):11753-11762. doi: 10.1021/acscatal.9b04107. Epub 2019 Nov 11.
6
Nitrene Radical Intermediates in Catalytic Synthesis.催化合成中的氮烯自由基中间体
Chemistry. 2017 Oct 9;23(56):13819-13829. doi: 10.1002/chem.201702537. Epub 2017 Sep 14.
7
Regiocontrolled synthesis of polysubstituted pyrroles starting from terminal alkynes, sulfonyl azides, and allenes.从末端炔烃、磺酰基叠氮化物和丙二烯出发，区域控制合成多取代吡咯。
Org Lett. 2013 Jul 5;15(13):3298-301. doi: 10.1021/ol401340u. Epub 2013 Jun 18.
8
Porphyrin Cobalt(III) "Nitrene Radical" Reactivity; Hydrogen Atom Transfer from Ortho-YH Substituents to the Nitrene Moiety of Cobalt-Bound Aryl Nitrene Intermediates (Y = O, NH).卟啉钴（III）“氮烯自由基”反应活性；从邻位YH取代基到钴结合芳基氮烯中间体氮烯部分的氢原子转移（Y = O，NH）
Molecules. 2016 Feb 20;21(2):242. doi: 10.3390/molecules21020242.
9
Designing catalysts for nitrene transfer using early transition metals and redox-active ligands.使用早期过渡金属和氧化还原活性配体设计氮烯转移催化剂。
Inorg Chem. 2011 Oct 17;50(20):9849-63. doi: 10.1021/ic200911b. Epub 2011 Jul 20.
10
Trimethylsilyl-Protected Alkynes as Selective Cross-Coupling Partners in Titanium-Catalyzed [2+2+1] Pyrrole Synthesis.三甲基硅基保护炔烃作为钛催化[2+2+1]吡咯合成中选择性交叉偶联伙伴。
Angew Chem Int Ed Engl. 2018 May 22;57(21):6090-6094. doi: 10.1002/anie.201800595. Epub 2018 Apr 25.
引用本文的文献
1
A Brief Introduction to Chemical Reaction Optimization.化学反应优化简介。
Chem Rev. 2023 Mar 22;123(6):3089-3126. doi: 10.1021/acs.chemrev.2c00798. Epub 2023 Feb 23.
2
A Synthetic Cycle for Heteroarene Synthesis by Nitride Insertion.通过氮化物插入合成杂芳烃的合成循环。
Angew Chem Int Ed Engl. 2022 Nov 14;61(46):e202213041. doi: 10.1002/anie.202213041. Epub 2022 Oct 18.
3
Synthesis of 1,2,4-azadiphosphole derivatives based on vanadium-catalyzed [2+2+1] cycloaddition reactions of azobenzenes with phosphaalkynes.基于钒催化偶氮苯与磷炔的[2+2+1]环加成反应合成1,2,4-氮杂二磷环戊烯衍生物
RSC Adv. 2020 Mar 30;10(22):12730-12733. doi: 10.1039/d0ra02503h.
4
Selective propargylic C(sp)-H activation of methyl-substituted alkynes [2 + 2] cycloaddition at a titanium imido template.在钛亚胺模板上对甲基取代的炔烃进行选择性炔丙基C(sp)-H活化及[2 + 2]环加成反应。
Chem Sci. 2021 Sep 28;12(41):13711-13718. doi: 10.1039/d1sc04334j. eCollection 2021 Oct 27.
5
Ti-Catalyzed and -Mediated Oxidative Amination Reactions.钛催化和介导的氧化氨化反应。
Acc Chem Res. 2021 Sep 7;54(17):3476-3490. doi: 10.1021/acs.accounts.1c00368. Epub 2021 Aug 22.
6
Multicomponent syntheses of 5- and 6-membered aromatic heterocycles using group 4-8 transition metal catalysts.使用第4-8族过渡金属催化剂进行5元和6元芳族杂环的多组分合成。
Chem Sci. 2021 Jun 29;12(28):9574-9590. doi: 10.1039/d1sc03037j. eCollection 2021 Jul 21.
7
Direct synthesis of pentasubstituted pyrroles and hexasubstituted pyrrolines from propargyl sulfonylamides and allenamides.由炔丙基磺酰胺和烯丙酰胺直接合成五取代吡咯和六取代吡咯啉
Chem Sci. 2021 Jun 8;12(26):9162-9167. doi: 10.1039/d1sc02090k. eCollection 2021 Jul 7.
8
A Mononuclear and High-Spin Tetrahedral Ti Complex.单核和高自旋四面体 Ti 配合物。
Inorg Chem. 2020 Dec 21;59(24):17834-17850. doi: 10.1021/acs.inorgchem.0c02586. Epub 2020 Dec 1.
9
Reactivity of terminal imido complexes of group 4-6 metals: stoichiometric and catalytic reactions involving cycloaddition with unsaturated organic molecules.4-6族金属末端亚胺配合物的反应活性：涉及与不饱和有机分子环加成的化学计量反应和催化反应。
Coord Chem Rev. 2020 Mar 15;407. doi: 10.1016/j.ccr.2019.213118. Epub 2020 Jan 14.
10
Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a BuP-P(SiMe) Ligand.溶剂对由BuP-P(SiMe)配体支撑的二苯基膦锂与Ti(III)配合物反应中产物多样性的影响。
Inorg Chem. 2020 Aug 17;59(16):11305-11315. doi: 10.1021/acs.inorgchem.0c00824. Epub 2020 Jul 31.
本文引用的文献
1
Catalytic Azoarene Synthesis from Aryl Azides Enabled by a Dinuclear Ni Complex.双核镍配合物促进的芳基叠氮化物的催化偶联反应。
J Am Chem Soc. 2018 Mar 21;140(11):4110-4118. doi: 10.1021/jacs.8b00503. Epub 2018 Mar 8.
2
Generation of Ti Alkyne Trimerization Catalysts in the Absence of Strong Metal Reductants.在无强金属还原剂情况下生成钛炔三聚催化剂。
Organometallics. 2017 Apr 10;36(7):1383-1390. doi: 10.1021/acs.organomet.7b00096. Epub 2017 Mar 29.
3
Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti[double bond, length as m-dash]NAd (Ad = adamantyl).氧化还原非无害性使得（二氮杂环丁二烯）钛[双键，键长如间位短划线]萘啶（Ad = 金刚烷基）能够催化氮宾羰基化反应。
Chem Sci. 2017 May 1;8(5):3410-3418. doi: 10.1039/c6sc05610e. Epub 2017 Mar 6.
4
Variable Time Normalization Analysis: General Graphical Elucidation of Reaction Orders from Concentration Profiles.变量时间归一化分析：从浓度分布中得出反应级数的一般图形说明。
Angew Chem Int Ed Engl. 2016 Dec 23;55(52):16084-16087. doi: 10.1002/anie.201609757. Epub 2016 Nov 25.
5
Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes.钛催化的炔烃与烯烃和重氮化合物的多组分氧化碳氨化反应。
J Am Chem Soc. 2016 Nov 9;138(44):14570-14573. doi: 10.1021/jacs.6b09939. Epub 2016 Oct 28.
6
A Simple Graphical Method to Determine the Order in Catalyst.一种确定催化剂中反应级数的简单图解法。
Angew Chem Int Ed Engl. 2016 Feb 5;55(6):2028-31. doi: 10.1002/anie.201508983. Epub 2016 Jan 8.
7
Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via Ti(II)/Ti(IV) redox catalysis.通过 Ti(II)/Ti(IV) 氧化还原催化，炔烃和重氮化合物催化形式[2+2+1]合成吡咯。
Nat Chem. 2016 Jan;8(1):63-8. doi: 10.1038/nchem.2386. Epub 2015 Nov 2.
8
Role of sterically demanding chiral dirhodium catalysts in site-selective C-H functionalization of activated primary C-H bonds.位阻手性二铑催化剂在活化一级 C-H 键的位点选择性 C-H 官能化反应中的作用。
J Am Chem Soc. 2014 Jul 9;136(27):9792-6. doi: 10.1021/ja504797x. Epub 2014 Jun 30.
9
Reduction of carbon dioxide promoted by a dinuclear tantalum tetrahydride complex.双核钽四氢化物配合物促进二氧化碳还原。
Inorg Chem. 2013 Feb 18;52(4):1685-7. doi: 10.1021/ic302438f. Epub 2013 Jan 29.
10
Group transfer reactions of d0 transition metal complexes: redox-active ligands provide a mechanism for expanded reactivity.d0 过渡金属配合物的基团转移反应：氧化还原活性配体提供了扩展反应性的机制。
Dalton Trans. 2013 Mar 21;42(11):3751-66. doi: 10.1039/c2dt32063k. Epub 2013 Jan 18.
Zotero 插件