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。
Reactivity of terminal imido complexes of group 4-6 metals: stoichiometric and catalytic reactions involving cycloaddition with unsaturated organic molecules.
作者信息
Kawakita Kento, Kakiuchi Yuya, Tsurugi Hayato, Mashima Kazushi, Parker Bernard F, Arnold John, Tonks Ian A
机构信息
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Department of Chemistry, University of California, Berkeley, California 94720, United States.
出版信息
Coord Chem Rev. 2020 Mar 15;407. doi: 10.1016/j.ccr.2019.213118. Epub 2020 Jan 14.
Abstract
Imido complexes of early transition metals are key intermediates in the synthesis of many nitrogen-containing organic compounds. The metal-nitrogen double bond of the imido moiety undergoes [2+2] cycloaddition reactions with various unsaturated organic molecules to form new nitrogen-carbon and nitrogen-heteroatom bonds. This review article focuses on reactivity of the terminal imido complexes of Group 4-6 metals, summarizing their stoichiometric reactions and catalytic applications for a variety of reactions including alkyne hydroamination, alkyne carboamination, pyrrole formation, imine metathesis, and condensation reactions of carbonyl compounds with isocyanates.
摘要
早期过渡金属的亚胺配合物是许多含氮有机化合物合成中的关键中间体。亚胺部分的金属-氮双键与各种不饱和有机分子发生[2+2]环加成反应，形成新的氮-碳键和氮-杂原子键。这篇综述文章重点关注第4-6族金属的末端亚胺配合物的反应活性，总结了它们在各种反应中的化学计量反应和催化应用，包括炔烃氢胺化、炔烃碳胺化、吡咯形成、亚胺复分解以及羰基化合物与异氰酸酯的缩合反应。
相似文献
1
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.
2
Enabling Nucleophilic Reactivity in High-Spin Fe(II) Imido Complexes: From Elementary Steps to Cooperative Catalysis.在高自旋Fe(II)亚胺配合物中实现亲核反应活性：从基本步骤到协同催化
Acc Chem Res. 2023 Dec 5;56(23):3392-3403. doi: 10.1021/acs.accounts.3c00511. Epub 2023 Nov 13.
3
Scandium Terminal Imido Chemistry.钪端亚氨基化学。
Acc Chem Res. 2018 Feb 20;51(2):557-566. doi: 10.1021/acs.accounts.7b00605. Epub 2018 Jan 30.
4
Selective transformations of organic compounds by imidozirconocene complexes.亚胺基锆茂络合物对有机化合物的选择性转化
Chem Rec. 2002;2(6):431-45. doi: 10.1002/tcr.10039.
5
Terminal imido rhodium complexes.末端脒基铑配合物。
Angew Chem Int Ed Engl. 2014 May 26;53(22):5614-8. doi: 10.1002/anie.201400023. Epub 2014 Apr 11.
6
Titanium-catalyzed multicomponent couplings: efficient one-pot syntheses of nitrogen heterocycles.钛催化的多组分偶联反应：氮杂环的高效一锅合成法。
Acc Chem Res. 2015 Nov 17;48(11):2822-33. doi: 10.1021/acs.accounts.5b00280. Epub 2015 Aug 21.
7
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.
8
Titanium hydrazido and imido complexes: synthesis, structure, reactivity, and relevance to alkyne hydroamination.钛酰肼和亚胺配合物：合成、结构、反应性及与炔烃氢胺化的相关性
J Am Chem Soc. 2004 Feb 18;126(6):1794-803. doi: 10.1021/ja038320g.
9
Regioselective [2+2] and [4+2] cycloaddition reactivity in an asymmetric niobium(bisimido) moiety towards unsaturated organic molecules.不对称铌（双亚胺）部分对不饱和有机分子的区域选择性[2+2]和[4+2]环加成反应活性。
Chem Commun (Camb). 2015 Jan 25;51(7):1278-81. doi: 10.1039/c4cc07851a.
10
Transition metal-carboryne complexes: synthesis, bonding, and reactivity.过渡金属-卡宾复合物：合成、键合和反应性。
Acc Chem Res. 2011 Apr 19;44(4):299-309. doi: 10.1021/ar100156f. Epub 2011 Mar 11.
引用本文的文献
1
Bonding and Reactivity of d Transition Metal Imido Complexes Encoded in Their N NMR Signatures.d过渡金属亚胺基配合物的键合与反应活性在其N核磁共振信号中的编码
J Am Chem Soc. 2024 Apr 10;146(14):9860-9870. doi: 10.1021/jacs.3c14723. Epub 2024 Mar 27.
2
Synthesis of Ti Complexes Supported by an ortho-terphenoxide Ligand and their Applications in Alkyne Hydroamination Catalysis.由邻三联苯氧基配体支撑的钛配合物的合成及其在炔烃氢胺化催化中的应用。
Organometallics. 2023 Jul 24;42(14):1732-1739. doi: 10.1021/acs.organomet.2c00593. Epub 2023 Feb 7.
3
A mononuclear, terminal titanium(III) imido.一种单核、末端的亚氨基三价钛。
Chem Commun (Camb). 2023 Aug 17;59(67):10101-10104. doi: 10.1039/d3cc01758c.
4
Reactivity and Structure of a Bis-phenolate Niobium NHC Complex.双酚氧基铌氮杂环卡宾配合物的反应活性与结构
ACS Org Inorg Au. 2022 Dec 5;3(1):59-71. doi: 10.1021/acsorginorgau.2c00028. eCollection 2023 Feb 1.
5
Engendering reactivity at group 5-heteroatom multiple bonds π-loading.在第5族杂原子多重键处引发反应性——π负载。
Chem Sci. 2022 Jun 29;13(28):8224-8242. doi: 10.1039/d2sc02706b. eCollection 2022 Jul 20.
6
Between imide, imidyl and nitrene - an imido iron complex in two oxidation states.在酰亚胺、亚胺基和氮烯之间——处于两种氧化态的一种亚胺铁配合物。
Chem Sci. 2022 Jun 9;13(26):7907-7913. doi: 10.1039/d2sc01088g. eCollection 2022 Jul 6.
7
α-Diimine synthesis titanium-mediated multicomponent diimination of alkynes with C-nitrosos.α-二亚胺合成：钛介导的炔烃与C-亚硝基的多组分二亚胺化反应
Chem Sci. 2021 Dec 27;13(5):1469-1477. doi: 10.1039/d1sc06111a. eCollection 2022 Feb 2.
8
N═N Bond Cleavage by Tantalum Hydride Complexes: Mechanistic Insights and Reactivity.氢化钽配合物引发的N═N键裂解：机理见解与反应活性
Inorg Chem. 2022 Jan 10;61(1):474-485. doi: 10.1021/acs.inorgchem.1c03152. Epub 2021 Dec 10.
9
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.
10
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.
本文引用的文献
1
In Situ Catalyst Generation and Benchtop-Compatible Entry Points for Ti/Ti Redox Catalytic Reactions.用于Ti/Ti氧化还原催化反应的原位催化剂生成及与台式设备兼容的切入点
Organometallics. 2018;37(23):4439-4445. doi: 10.1021/acs.organomet.8b00474. Epub 2018 Sep 6.
2
Dative Directing Group Effects in Ti-Catalyzed [2+2+1] Pyrrole Synthesis: Chemo- and Regioselective Alkyne Heterocoupling.钛催化[2+2+1]吡咯合成中的给体导向基团效应：化学和区域选择性炔烃杂偶联
ACS Catal. 2019 Jan 4;9(1):216-223. doi: 10.1021/acscatal.8b04669. Epub 2018 Nov 29.
3
Rare-earth metal and actinide organoimide chemistry.稀土金属和锕系元素有机亚胺化学。
Chem Soc Rev. 2019 Dec 9;48(24):5752-5805. doi: 10.1039/c8cs00932e.
4
Bis(imido)vanadium(V)-Catalyzed [2+2+1] Coupling of Alkynes and Azobenzenes Giving Multisubstituted Pyrroles.双(亚胺基)钒(V)催化炔烃和偶氮苯的[2+2+1]偶联反应生成多取代吡咯。
J Am Chem Soc. 2019 Mar 13;141(10):4194-4198. doi: 10.1021/jacs.8b13390. Epub 2019 Feb 11.
5
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.
6
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.
7
The Mechanism of the [Cp TiMe ]-Catalyzed Intermolecular Hydroamination of Alkynes.[CpTiMe]催化的炔烃分子间氢胺化反应的机理
Angew Chem Int Ed Engl. 2001 Jun 18;40(12):2305-2308. doi: 10.1002/1521-3773(20010618)40:12<2305::AID-ANIE2305>3.0.CO;2-7.
8
Strong Preference of the Redox-Neutral Mechanism over the Redox Mechanism for the Ti Catalysis Involved in the Carboamination of Alkyne with Alkene and Diazene.Ti 催化炔烃与烯烃和叠氮化物的碳氨化反应中，氧化还原中性机制相对于氧化还原机制的强烈偏好。
Chemistry. 2018 May 11;24(27):7010-7025. doi: 10.1002/chem.201800339. Epub 2018 Apr 30.
9
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.
10
Metathesis cleavage of an N[double bond, length as m-dash]N bond in benzo[c]cinnolines and azobenzenes by triply-bonded ditungsten complexes.三键合二钨配合物引发苯并[c]肉桂啶和偶氮苯中 N[双键，长度为破折号]N 键的易位断裂。
Chem Commun (Camb). 2018 Apr 10;54(30):3709-3711. doi: 10.1039/c7cc08570b.
Zotero 插件