Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts
Abstract
:1. Introduction
2. Results and Discussion
2.1. Concept for the Synthesis of Electronically Modified Neutral Ru-Based 16 VE Allenylidene Complexes
2.2. Synthesis of Electronically Modified Propargyl Alcohols 8a–c
2.3. Synthesis of Ru-Precatalysts 5a–c
2.4. Reactivities of the New Precatalysts
3. Experimental
3.1. General
3.2. General Procedure for the Synthesis of Propargyl Alcohols 8a–c
3.3. General Procedure for the Synthesis of the Precatalysts 5a–c
4. Conclusions
- Samples Availability: Not available.
References
- Nicolaou, K.C.; Bulger, P.G.; Sarlah, D. Metathesis Reactions in Total Synthesis. Angew. Chem. Int. Ed. 2005, 44, 4490–4527. [Google Scholar] [CrossRef]
- Fürstner, A. Metathesis in total synthesis. Chem. Commun. 2011, 47, 6505–6511. [Google Scholar] [CrossRef]
- Lozano-Vila, A.M.; Monsaert, S.; Bajek, A.; Verpoort, F. Ruthenium-Based Olefin Metathesis Catalysts Derived from Alkynes. Chem. Rev. 2010, 110, 4865–4909. [Google Scholar] [CrossRef]
- Vougioukalakis, G.C.; Grubbs, R.H. Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts. Chem. Rev. 2009, 110, 1746–1787. [Google Scholar] [CrossRef]
- Samojłowicz, C.; Bieniek, M.; Grela, K. Ruthenium-Based Olefin Metathesis Catalysts Bearing N-Heterocyclic Carbene Ligands. Chem. Rev. 2009, 109, 3708–3742. [Google Scholar] [CrossRef]
- Deshmukh, P.H.; Blechert, S. Alkene metathesis: the search for better catalysts. Dalton Trans. 2007, 2479–2491. [Google Scholar] [CrossRef]
- Zaja, M.; Connon, S.J.; Dunne, A.M.; Rivard, M.; Buschmann, N.; Jiricek, J.; Blechert, S. Ruthenium olefin metathesis catalysts with modified styrene ethers: influence of steric and electronic effects. Tetrahedron 2003, 59, 6545–6558. [Google Scholar] [CrossRef]
- Grela, K.; Harutyunyan, S.; Michrowska, A. A Highly Efficient Ruthenium Catalyst for Metathesis Reactions. Angew. Chem. Int. Ed. 2002, 41, 4038–4040. [Google Scholar] [CrossRef]
- Antonucci, A.; Bassetti, M.; Bruneau, C.; Dixneuf, P.H.; Pasquini, C. Allenylidene to Indenylidene Rearrangement in Cationic p-Cymene Ruthenium(II) Complexes: Solvent, Counteranion, and Substituent Effects in the Key Step toward Catalytic Olefin Metathesis. Organometallics 2010, 29, 4524–4531. [Google Scholar] [CrossRef]
- Semeril, D.; Olivier-Bourbigou, H.; Bruneau, C.; Dixneuf, P.H. Alkene metathesis catalysis in ionic liquids with ruthenium allenylidene salts. Chem. Commun. 2002, 146–147. [Google Scholar]
- Fürstner, A.; Liebl, M.; Lehmann, C.W.; Picquet, M.; Kunz, R.; Bruneau, C.; Touchard, D.; Dixneuf, P.H. Cationic Ruthenium Allenylidene Complexes as Catalysts for Ring Closing Olefin Metathesis. Chem. Eur. J. 2000, 6, 1847–1857. [Google Scholar] [CrossRef]
- Costin, S.; Widaman, A.K.; Rath, N.P.; Bauer, E.B. Synthesis and Structural Characterization of a Series of New Chiral-at-Metal Ruthenium Allenylidene Complexes. Eur. J. Inorg. Chem. 2011, 1269–1282. [Google Scholar]
- Kabro, A.; Ghattas, G.; Roisnel, T.; Fischmeister, C.; Bruneau, C. New ruthenium metathesis catalysts with chelating indenylidene ligands: Synthesis, characterization and reactivity. Dalton Trans. 2012, 41, 3695–3700. [Google Scholar] [CrossRef]
- Kabro, A.; Roisnel, T.; Fischmeister, C.; Bruneau, C. Ruthenium-Indenylidene Olefin Metathesis Catalyst with Enhanced Thermal Stability. Chem. Eur. J. 2010, 16, 12255–12261. [Google Scholar] [CrossRef]
- Schanz, H.-J.; Jafarpour, L.; Stevens, E.D.; Nolan, S.P. Coordinatively Unsaturated 16-Electron Ruthenium Allenylidene Complexes: Synthetic, Structural, and Catalytic Studies. Organometallics 1999, 18, 5187–5190. [Google Scholar] [CrossRef]
- Selegue, J.P. Synthesis and structure of [Ru(C3Ph2)(PMe3)2(Cp)][PF6], a cationic diphenylallenylidene complex. Organometallics 1982, 1, 217–218. [Google Scholar]
- Harlow, K.J.; Hill, A.F.; Wilton-Ely, D.E.T.J. The first co-ordinatively unsaturated Group 8 allenylidene complexes: Insights into Grubbs’ vs. Dixneuf-Fürstner olefin metathesis catalysts. J. Chem. Soc. Dalton Trans. 1999, 285–292. [Google Scholar]
- Fürstner, A.; Guth, O.; Düffels, A.; Seidel, G.; Liebl, M.; Gabor, B.; Mynott, R. Indenylidene Complexes of Ruthenium: Optimized Synthesis, Structure Elucidation, and Performance as Catalysts for Olefin Metathesis—Application to the Synthesis of the ADE-Ring System of Nakadomarin A. Chem. Eur. J. 2001, 7, 4811–4820. [Google Scholar] [CrossRef]
- Fürstner, A.; Grabowski, J.; Lehmann, C.W. Total Synthesis and Structural Refinement of the Cyclic Tripyrrole Pigment Nonylprodigiosin. J. Org. Chem. 1999, 64, 8275–8280. [Google Scholar] [CrossRef]
- Shaffer, E.A.; Chen, C.-L.; Beatty, A.M.; Valente, E.J.; Schanz, H.-J. Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation. J. Organomet. Chem. 2007, 692, 5221–5233. [Google Scholar] [CrossRef]
- Dragutan, V.; Dragutan, I.; Verpoort, F. Ruthenium Indenylidene Complexes. Platinum Metals Rev. 2005, 49, 33–40. [Google Scholar] [CrossRef]
- Dragutan, I.; Dragutan, V. Ruthenium Allenylidene Complexes. Platinum Metals Rev. 2006, 50, 81–97. [Google Scholar] [CrossRef]
- Castarlenas, R.; Dixneuf, P.H. Highly Active Catalysts in Alkene Metathesis: First Observed Transformation of Allenylidene into Indenylidene via Alkenylcarbyne—Ruthenium Species. Angew. Chem. Int. Ed. 2003, 42, 4524–4527. [Google Scholar] [CrossRef]
- McFarland, J.W.; Lenz, D.E.; Grosse, D.J. The Chemistry of Sulfonyl Isocyanates. III. Reactions with Triarylcarbinols. J. Org. Chem. 1966, 31, 3798–3800. [Google Scholar] [CrossRef]
- Dilthey, W.; Quint, F.; Dierichs, H. Zur Kenntnis der Oxydation von Carbeniumsalzen mit Wasserstoffsuperoxyd. [Pyrenium, XXXI]. J. für Praktische Chemie 1938, 151, 25–34. [Google Scholar]
- Fischer, O.; Hess, W. Zur Kenntniss der Ketonspaltung bei den Triphenylcarbinolen. Chem. Ber. 1905, 38, 335–338. [Google Scholar] [CrossRef]
- Fürstner, A.; Liebl, M.; Hill, A.F.; Wilton-Ely, J.D.E.T. Coordinatively unsaturated ruthenium allenylidene complexes: highly effective, well defined catalysts for the ring-closure metathesis of α,ω-dienes and dienynes. Chem. Commun. 1999, 601–602. [Google Scholar]
- Gabbutt, C.D.; Heron, B.M.; Instone, A.C.; Thomas, D.A.; Partington, S.M.; Hursthouse, M.B.; Gelbrich, T. Observations on the Synthesis of Photochromic Naphthopyrans. Eur. J. Org. Chem. 2003, 1220–1230. [Google Scholar]
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Lichtenheldt, M.; Kress, S.; Blechert, S. Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts. Molecules 2012, 17, 5177-5186. https://doi.org/10.3390/molecules17055177
Lichtenheldt M, Kress S, Blechert S. Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts. Molecules. 2012; 17(5):5177-5186. https://doi.org/10.3390/molecules17055177
Chicago/Turabian StyleLichtenheldt, Martin, Steffen Kress, and Siegfried Blechert. 2012. "Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts" Molecules 17, no. 5: 5177-5186. https://doi.org/10.3390/molecules17055177