Ate Complexes in Iron-Catalyzed Cross-Coupling Reactions

被引：36

作者：

Parchomyk, Tobias ^{[1
]}

Koszinowski, Konrad ^{[1
]}

机构：

[1] Georg August Univ Gottingen, Inst Organ & Biomol Chem, Tammannstr 2, D-37077 Gottingen, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 44期

关键词：

cross coupling; gas-phase reactions; iron; mass spectrometry; reaction mechanisms; ARYL-GRIGNARD-REAGENTS; ALKYL-HALIDES; GAS-PHASE; MASS-SPECTROMETRY; REACTIVITY; NUCLEOPHILES; ASSOCIATION; REDUCTION; KUMADA; TMEDA;

D O I：

10.1002/chem.201603574

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Iron-catalyzed cross-coupling reactions have an outstanding potential for sustainable organic synthesis, but remain poorly understood mechanistically. Here, we use electrospray-ionization (ESI) mass spectrometry to identify the ionic species formed in these reactions and characterize their reactivity. Transmetalation of Fe(acac)(3) (acac=acetylacetonato) with PhMgCl in THF (tetrahydrofuran) produces anionic iron ate complexes, whose nuclearity (1 to 4Fe centers) and oxidation states (ranging from -I to +III) crucially depend on the presence of additives or ligands. Upon addition of iPrCl, formation of the heteroleptic Fe-III complex [Ph3Fe(iPr)](-) is observed. Gas-phase fragmentation of this complex results in reductive elimination and release of the cross-coupling product with high selectivity.

引用

页码：15609 / 15613

页数：5

共 49 条

[1] Iron(I) in Negishi Cross-Coupling Reactions [J].

Adams, Christopher J. ;

Bedford, Robin B. ;

Carter, Emma ;

Gower, Nicholas J. ;

Haddow, Mairi F. ;

Harvey, Jeremy N. ;

Huwe, Michael ;

Angeles Cartes, M. ;

Mansell, Stephen M. ;

Mendoza, Carla ;

Murphy, Damien M. ;

Neeve, Emily C. ;

Nunn, Joshua .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (25) :10333-10336

[2] Isolation and Characterization of a Tetramethyliron(III) Ferrate: An Intermediate in the Reduction Pathway of Ferric Salts with MeMgBr [J].

Al-Afyouni, Malik H. ;

Fillman, Kathlyn L. ;

Brennessel, William W. ;

Neidig, Michael L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (44) :15457-15460

[3]

Andris E., 2016, Angew. Chem. Int. Ed, V128, P3701, DOI 10.1002/ange.201511374

[4] Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase [J].

Andris, Erik ;

Jasik, Juraj ;

Gomez, Laura ;

Costas, Miquel ;

Roithova, Jana .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (11) :3637-3641

[5]

[Anonymous], 2000, ANGEW CHEM

[6]

Bedford R. B., 2014, ANGEW CHEM, V126, P1835

[7] The influence of the ligand chelate effect on iron-amine-catalysed Kumada cross-coupling [J].

Bedford, Robin B. ;

Brenner, Peter B. ;

Elorriaga, David ;

Harvey, Jeremy N. ;

Nunn, Joshua .

DALTON TRANSACTIONS, 2016, 45 (40) :15811-15817

[8] How Low Does Iron Go? Chasing the Active Species in Fe-Catalyzed Cross-Coupling Reactions [J].

Bedford, Robin B. .

ACCOUNTS OF CHEMICAL RESEARCH, 2015, 48 (05) :1485-1493

[9] Iron Phosphine Catalyzed Cross-Coupling of Tetraorganoborates and Related Group 13 Nucleophiles with Alkyl Halides [J].

Bedford, Robin B. ;

Brenner, Peter B. ;

Carter, Emma ;

Clifton, Jamie ;

Cogswell, Paul M. ;

Gower, Nicholas J. ;

Haddow, Mairi F. ;

Harvey, Jeremy N. ;

Kehl, Jeffrey A. ;

Murphy, Damien M. ;

Neeve, Emily C. ;

Neidig, Michael L. ;

Nunn, Joshua ;

Snyder, Benjamin E. R. ;

Taylor, Joseph .

ORGANOMETALLICS, 2014, 33 (20) :5767-5780

[10] TMEDA in Iron-Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic "ate" Complex Formation [J].

Bedford, Robin B. ;

Brenner, Peter B. ;

Carter, Emma ;

Cogswell, Paul M. ;

Haddow, Mairi F. ;

Harvey, Jeremy N. ;

Murphy, Damien M. ;

Nunn, Joshua ;

Woodall, Christopher H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (07) :1804-1808

← 1 2 3 4 5 →