Iron Catalyzed Cross Coupling: Mechanism and Application. Matthew Burk Denmark Group Meeting
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1 Iron Catalyzed Cross Coupling: Mechanism and Application Matthew Burk Denmark Group Meeting
2 Long Induction Period: Early History Of Iron Catalyzed Cross Coupling 1941: Effect of metal impurities on homocoupling during Grignard formation investigated by Kharasch Followed by coupling of alkyl Grignards with benzyl bromide (1945), acetyl chloride (1953) 1971:Extensive studies on coupling with vinyl halides by Kochi : Occasional reports, including use of vinyl halides (1983) and allylic phosphonates (1991) 1998:Cahiez reports practical method of coupling alkyl Grignardsand vinyl halides 2002: Fürstner reports highly practical coupling of alkyl Grignards with aryl halides 2002-present: Many reports by many groups. Kharasch, M. S.; Fields, E. K. J. Am. Chem. Soc. 1941, 63, Vavon, G.; Chaminade, C.; Quesnel, G. Hebd. Seances Acad. Sci. 1945, 220, Tamura, M.; Kochi, J. K. Vinylation of Grignard reagents. Catalysis by iron. J. Am. Chem. Soc. 1971, 93, Molander, G. A.; Rahn, B. J.; Shubert, D. C.; Bonde, S. E.; Tet. Lett. 1983, 5449 Yanagisawa, A.; Nomura, N. Yamamoto, H. Synlett, 1991, 514 Fürstner, A.; Leitner, A.; Mendez, M.; Krause, H. JACS, 2002, 124, 13856
3 Cross-Coupling of Vinyl Halides: Overview Earliest studies: Kochi Molander s Modification Stereospecific Drawback: Several equiv. of bromide used 1:1 Stoichiometry E-bromides give E,Z mixtures Cahiez s Modification Broad scope Stereospecific Insensitive to choice of halide Tamura, M.; Kochi, J. K. JACS, 1971, 93, Molander, G. A.; Rahn, B. J.; Shubert, D. C.; Bonde, S. E.; Tet. Lett. 1983, 5449 Cahiez, G.; Avedissian, H. Synthesis, 1998, 1199
4 Alkylation of Aryl Halides Electron-poor aryl chlorides and alkyl Grignards are excellent coupling partners Electron rich arenes require OTf Fürstner, A.; Leitner, A.; Mendez, M.; Krause, H. JACS, 2002, 124, 13856
5 Arylation of Aryl Halides More challenging, homocoupling of Grignard problematic Two methods known: FeF 3 suppresses homocoupling Catalyst pretreated with EtMgBr@ 0 23 C for 4 h Thermal stability of active species is remarkable Hatakeyama, T.; Nakamura, M. JACS, 2007, 129, Sapountzis, I.; Lin, W.; Kofink, C.; Despotoulou, C.; Knochel, P. ACIE, 2005, 44, Kofink, C.; Blank, B.; Pagano, S.; Götz, N.; Knochel, P.; ChemComm, 2007, Electron-rich iodides are unreactive
6 Cross Coupling of Alkyl Halides Arylation of Alkyl Halides Amine ligands Preformed Fe (-2) complex (Much more on this later) 8= Alkylation of Alkyl Halides Nakamura, M.; Matsuo, K.; Ito, S.; Nakamura, E. JACS, 2004, 126, Martin, R.; Fürstner, A.; Angew. Chem., 2004, 116, Dongol, K.; Koh, H.; Sau, M.; Chai, C. Adv. Synth. Catal.2007, 349, 1015
7 Cross Coupling of Vinyl Halides: Kochi s pioneering studies K=k[MeMgBr] 0 [bromide] 1 Poor results obtained with higher alkyl Grignards due to elimination, homocoupling and reduction. Measures all conversions based on Grignard reagent Proposes a Fe(I)-Fe(III) cycle (but won t rule out Fe(0)-Fe(II)) Evidence: analysis of headspace gases (1.5 to 2.0 equiv MeMgBr consumed during catalyst activation) ESR of activated complex formed from EtMgBr+ Fe(dbm) 3 shows broad signal at <g>=2.085 Determined that dbm(and acac) ligands are reduced to radical dianions, disproving his interpretation of UV/Vis spectra. Smith, R. S.; Kochi, J. K. JOC, 1976, 41, 502. Tamura, M.; Kochi, J. K. JACS, 1971, 93, Neumann, S. M.; Kochi, J. K. JOC, 1975, 40,599. Kwan, C. L.; Kochi, J. K. JACS, 1976, 98, 4903.
8 Problem Propose an alternative oxidation state (not Fe(I)) for Kochi s intermediate that explains the total stoichiometry (n) of gases observed during catalyst activation.
9 Mechanisms of Iron Catalyzed Cross-coupling The Fürstnermodel: at least two classes of mechanisms exist (<0 to -20 C) Fe(0) Fe(-II) cycle: [Fe(MgX) 2 ] n, aka inorganic Grignard Black-brown, unstable solutions Requires β-hydride elimination or other initiation mechanism Fe(II) Ferrate, aka Super-ate complex: Bright yellow solutions Occurs in absence of β-hydride e.g. MeMgBr Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773
10 Evidence for Ferrate Manifold Different Reactivity of MeMgBr: O TfO O Me O O 70% O X-ray structure of Li analog A: A THF,-30 C Cl Cl O Me 60% Cl A O OMe X X=Cl, I, OTf X O OMe <20% Fürstner, A.; Krause, H.; Lehmann, C.; Angew. Chem., 2006,118,454
11 Complications with Phenyl Analogs Both decompose thermally, producing biphenyl Bazhenova, T; Lobkovskaya, R.; Shibaeva, R.; Shilov, A. Shilova, A.; Gruselle, M.; Leny, G.; Tchoubar, B. J. Organomet. Chem , 265. Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773
12 Non-Ferrate Manifold Active catalyst is not stable (except in under certain conditions) Wide range of plausible oxidation states Model systems required Mechanistic Hypothesis: Active catalyst is Mg/Fe clusters of composition [Fe(MgX) 2 ] n Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773 Jonas, K. ACIE, , 295.
13 Stoichiometric σ-bond Metathesis in Model Systems Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773 Hill, D.; Parvez, M.; Sen, A.; JACS 1994,
14 Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS2008, 130, 8773 Potential Fe(I)-Fe(III) cycle
15 Relative Catalytic Activity of Model Complexes Only 8(Fe(-II)) accounts for very high rates observed in catalytic reactions Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773
16 Catalytic activity of complexes Selected examples: A= Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773
17 Evidence for Radical Intermediate 8= Evidence against: no reaction with 3 halides Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. JACS 2008, 130, 8773 Hölzer, B. Hoffman, Reinhard W. ChemComm, 2003, 732. Hill, D.; Parvez, M.; Sen, A.; JACS 1994,
18 Conclusions Iron-catalyzed cross couplings at low temperature likely occur by an Fe(-II) catalyzed process, preceded by catalyst activation through a β-hydride elimination/reductive elimination pathway. An alternative Fe(I) Fe(III) cycle appears to be too slow to account for the observed catalytic rates, but could possibly participate under some combination of conditions. In the absence of a β-hydride on the Grignard reagent, the active species may be a tetraalkyl ferrate (Fe(II)) Insertion into alkyl C-X bonds involves a radical intermediate. At higher temperatures (>-20 to 0 C) little is known.
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