Iron‐Catalyzed Isomerizations of Olefins

Mayer, Michael; Welther, Alice; Wangelin, Axel Jacobi von

doi:10.1002/cctc.201100207

Cited by 110 publications

(51 citation statements)

References 51 publications

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“…6 Recently, the olefin isomerization reaction has been highlighted as a very useful method to synthesize many desired targets. 7 Catalysts containing a broad range of transition metals, including Cr, 8 Fe, 9,10 Co, 11,12 Pd, 13−15 Ni, 13 Rh, 16 Ir, 17 Pt, 18 Zr, 19 and Ru, 20−23 have been developed to facilitate olefin isomerization. Most such studies, however, focus on the migration of nonconjugated double bonds.…”

Section: Introductionmentioning

confidence: 99%

DFT Studies on the Reaction Mechanism of 1,3-Conjugated Dienes Isomerization Catalyzed by Ruthenium Hydride

et al. 2015

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The detailed reaction mechanism for the isomerization of 1,3-conjugated dienes catalyzed by the ruthenium hydride complex RuHCl(CO)(H 2 IMes)(PCy 3 ) has been studied with the aid of density functional theory (DFT) calculations. Both cis and trans isomers of a 1,3-conjugated diene were considered as the reactants. For each isomer, two catalytic cycles were calculated, which (respectively) generate a 1,3-hydride shift product or a 1,5-hydride shift product. Both catalytic cycles proceed via alkene migratory insertion into the Ru−H bond, σ-allyl ruthenium isomerization, and β-H elimination steps. Our computational study shows that the cis isomer of the model reactant reacts preferentially via the pathway leading to the 1,5-hydride shift product, consistent with the experimental results. The σ-allyl ruthenium isomerization step is found to be crucial for reaction regioselectivity. Strong binding of the CC bond to Ru is involved in the generation of the 1,5-hydride shift product. In addition, the steric effect of the bulky N-heterocyclic carbene ligand in ruthenium hydride RuHCl(CO)(H 2 IMes)(PCy 3 ) was considered theoretically.

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Section: Introductionmentioning

confidence: 99%

DFT Studies on the Reaction Mechanism of 1,3-Conjugated Dienes Isomerization Catalyzed by Ruthenium Hydride

et al. 2015

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“…[12] Other examples are the isomerisation of allyl benzenes such as estragol or safrole, which are of great interest for the fragrance industry. [13,14] A wide range of isomerisation catalysts have been developed based on various metals such as Pd, [15][16][17] Ru, [18][19][20][21][22] Ti, [23][24][25] V, [26] Fe, [27][28][29] Rh, [30][31][32] Mo, [33] Ni, [34][35][36] etc., but also metal-free systems such as frustrated Lewis pairs. [37] One of the most active catalysts is the ruthenium-based "alkene zipper" developed by Grotjahn and co-workers.…”

Section: Introductionmentioning

confidence: 99%

Alkene Isomerisation Catalysed by a Ruthenium PNN Pincer Complex

Perdriau

Chang

Otten

et al. 2014

Chemistry A European J

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The [Ru(CO)H(PNN)] pincer complex based on a dearomatised PNN ligand (PNN: 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) was examined for its ability to isomerise alkenes. The isomerisation reaction proceeded under mild conditions after activation of the complex with alcohols. Variable-temperature (VT) NMR experiments to investigate the role of the alcohol in the mechanism lend credence to the hypothesis that the first step involves the formation of a rearomatised alkoxide complex. In this complex, the hemilabile diethylamino side-arm can dissociate, allowing alkene binding cis to the hydride, enabling insertion of the alkene into the metal-hydride bond, whereas in the parent complex only trans binding is possible. During this study, a new uncommon Ru(0) coordination complex was also characterised. The scope of the alkene isomerisation reaction was examined.

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“…Thermodynamic migration to the highersubstituted olefin products was not observed (entries 8-15, 18, and 19). [9] Homogeneous and heterogeneous catalysis mechanisms can be distinguished by kinetic experiments. [10] Quantitative analyses of the model reaction between 1 and 2 documented an extremely rapid onset of catalyst activity even between À35 and 0 8 8Cw ithout induction periods or sigmoidal curves, which could indicate nanocluster nucleations en route to particle formation.…”

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confidence: 99%

Iron‐Catalyzed Cross‐Coupling of Alkenyl Acetates

et al. 2015

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Stable C-O linkages are generally unreactive in cross-coupling reactions which mostly employ more electrophilic halides or activated esters (triflates, tosylates). Acetates are cheap and easily accessible electrophiles but have not been used in cross-couplings because the strong C-O bond and high propensity to engage in unwanted acetylation and deprotonation. Reported herein is a selective iron-catalyzed cross-coupling of diverse alkenyl acetates, and it operates under mild reaction conditions (0 °C, 2 h) with a ligand-free catalyst (1-2 mol%).

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Iron‐Catalyzed Isomerizations of Olefins

Cited by 110 publications

References 51 publications

DFT Studies on the Reaction Mechanism of 1,3-Conjugated Dienes Isomerization Catalyzed by Ruthenium Hydride

DFT Studies on the Reaction Mechanism of 1,3-Conjugated Dienes Isomerization Catalyzed by Ruthenium Hydride

Alkene Isomerisation Catalysed by a Ruthenium PNN Pincer Complex

Iron‐Catalyzed Cross‐Coupling of Alkenyl Acetates

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