Grubbs' catalyst

First-generation Grubbs catalyst
Names
IUPAC name
Benzylidene-bis(tricyclohexylphosphino)-dichlororuthenium
Identifiers
3D model (JSmol)
Properties
C43H72Cl2P2Ru
Molar mass 822.96 g·mol−1
Appearance Purple solid
Melting point 153 °C (307 °F; 426 K) (decomposition)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Second-generation Grubbs catalyst
Names
IUPAC name
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphino)ruthenium
Identifiers
Properties
C46H65Cl2N2PRu
Molar mass 848,97 g·mol−1
Appearance Pinkish brown solid
Melting point 143.5 to 148.5 °C (290.3 to 299.3 °F; 416.6 to 421.6 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
First-generation Hoveyda–Grubbs catalyst
Names
IUPAC name
Dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II)
Identifiers
Properties
C28H45Cl2OPRu
Molar mass 600.61 g·mol−1
Appearance Brown solid
Melting point 195 to 197 °C (383 to 387 °F; 468 to 470 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Second-generation Hoveyda–Grubbs catalyst
Names
IUPAC name
[1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isopropoxyphenylmethylene)ruthenium
Identifiers
Properties
C31H38Cl2N2ORu
Molar mass 626.62 g·mol−1
Appearance Green solid
Melting point 216 to 220 °C (421 to 428 °F; 489 to 493 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Grubbs' catalysts are a series of transition metal carbene complexes used as catalysts for olefin metathesis. They are named after Robert H. Grubbs, the chemist who supervised their synthesis. Several generations of the catalyst have been developed.[1][2] Grubbs' catalysts tolerate many functional groups in the alkene substrates, are air-tolerant, and are compatible with a wide range of solvents.[3][4] For these reasons, Grubbs' catalysts have become popular in synthetic organic chemistry.[5] Grubbs, together with Richard R. Schrock and Yves Chauvin, won the Nobel Prize in Chemistry in recognition of their contributions to the development of olefin metathesis.

First-generation catalyst

In the 1960s, ruthenium trichloride was found to catalyze olefin metathesis. Processes were commercialized based on these discoveries. These ill-defined but highly active homogeneous catalysts remain in industrial use.[6] The first well-defined ruthenium catalyst was reported in 1992.[7] It was prepared from RuCl2(PPh3)4 and diphenylcyclopropene.

This initial ruthenium catalyst was followed in 1995 by what is now known as the first-generation Grubbs catalyst. It is synthesized from RuCl2(PPh3)3, phenyldiazomethane, and tricyclohexylphosphine in a one-pot synthesis.[8][9]

The first-generation Grubbs catalyst was the first well-defined Ru-based catalyst. It is also important as a precursor to all other Grubbs-type catalysts.

Second-generation catalyst

The second-generation catalyst has the same uses in organic synthesis as the first generation catalyst, but generally with higher activity. This catalyst is stable toward moisture and air, thus is easier to handle in the lab.

Shortly before the discovery of the second-generation Grubbs catalyst, a very similar catalyst based on an unsaturated N-heterocyclic carbene (1,3-bis(2,4,6-trimethylphenyl)imidazole) was reported independently by Nolan[10] and Grubbs[11] in March 1999, and by Fürstner[12] in June of the same year. Shortly thereafter, in August 1999, Grubbs reported the second-generation catalyst, based on a saturated N-heterocyclic carbene (1,3-bis(2,4,6-trimethylphenyl)dihydroimidazole):[13]

In both the saturated and unsaturated cases a phosphine ligand is replaced with an N-heterocyclic carbene (NHC), which is characteristic of all second-generation-type catalysts.[3]

Both the first- and second-generation catalysts are commercially available, along with many derivatives of the second-generation catalyst.

Hoveyda–Grubbs catalysts

In the Hoveyda–Grubbs catalysts, the benzylidene ligands have a chelating ortho-isopropoxy group attached to the benzene rings. The ortho-isopropoxybenzylidene moiety is sometimes referred to as a Hoveyda chelate. The chelating oxygen atom replaces a phosphine ligand, which in the case of the 2nd generation catalyst, gives a completely phosphine-free structure. The 1st generation Hoveyda–Grubbs catalyst was reported in 1999 by Amir H. Hoveyda's group,[14] and in the following year, the second-generation Hoveyda–Grubbs catalyst was described in nearly simultaneous publications by the Blechert[15] and Hoveyda[16] laboratories. Siegfried Blechert's name is not commonly included in the eponymous catalyst name. The Hoveyda–Grubbs catalysts, while more expensive and slower to initiate than the Grubbs catalyst from which they are derived, are popular because of their improved stability.[3] By changing the steric and electronic properties of the chelate, the initiation rate of the catalyst can be modulated,[17] such as in the Zhan Catalysts. Hoveyda–Grubbs catalysts are easily formed from the corresponding Grubbs catalyst by the addition of the chelating ligand and the use of a phosphine scavenger like copper(I) chloride:[16]

The second-generation Hoveyda–Grubbs catalysts can also be prepared from the 1st generation Hoveyda–Grubbs catalyst by the addition of the NHC:[15]

In one study a water-soluble Grubbs catalyst is prepared by attaching a polyethylene glycol chain to the imidazolidine group.[18] This catalyst is used in the ring-closing metathesis reaction in water of a diene carrying an ammonium salt group making it water-soluble as well.

Third-generation Grubbs catalyst (Fast-initiating catalysts)

The rate of the Grubbs catalyst can be altered by replacing the phosphine ligand with more labile pyridine ligands. By using 3-bromopyridine the initiation rate is increased more than a millionfold.[19] Both pyridine and 3-bromopyridine are commonly used, with the bromo- version 4.8 time more liable resulting in fast rates.[20] The catalyst is traditionally isolated as a two pyridine complex, however one pyridine is lost upon dissolving and reversibly inhibits the ruthenium center throughout any chemical reaction.

The principle application of the fast-initiating catalysts is as initiators for ring opening metathesis polymerisation (ROMP). Because of their usefulness in ROMP these catalysts are sometimes referred to as the 3rd generation Grubbs' catalysts.[21] The high ratio of the rate of initiation to the rate of propagation makes these catalysts useful in living polymerization, yielding polymers with low polydispersity.[22]

Applications

Grubbs' catalysts are of interest for olefin metathesis. It is mainly applied to fine chemical synthesis. Large-scale commercial applications of olefin metathesis almost always employ heterogeneous catalysts or ill-defined systems based on ruthenium trichloride.[6]

References

  1. ↑ Grubbs, Robert H. (2003). Handbook of Metathesis (1st ed.). Weinheim: Wiley-VCH. ISBN 3-527-30616-1.
  2. ↑ Grubbs, R. H.; Trnka, T. M. (2004). "Ruthenium-Catalyzed Olefin Metathesis". In Murahashi, S. Ruthenium in Organic Synthesis. Weinheim: Wiley-VCH. doi:10.1002/3527603832.ch6.
  3. 1 2 3 Vougioukalakis, G. C.; Grubbs, R. H. (2010). "Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts". Chem. Rev. 110 (3): 1746–1787. doi:10.1021/cr9002424. PMID 20000700.
  4. ↑ Trnka, T. M.; Grubbs, R. H. (2001). "The Development of L2X2Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story". Acc. Chem. Res. 34 (1): 18–29. doi:10.1021/ar000114f. PMID 11170353.
  5. ↑ Cossy, Janine; Arseniyadis, Stellios; Meyer, Christophe (2010). Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts (1st ed.). Weinheim: Wiley-VCH. ISBN 3-527-32440-2.
  6. 1 2 Lionel Delaude, Alfred F. Noels (2005). "Metathesis". Kirk-Othmer Encyclopedia of Chemical Technology. Weinheim: Wiley-VCH. doi:10.1002/0471238961.metanoel.a01.
  7. ↑ Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. (1992). "Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media". J. Am. Chem. Soc. 114 (10): 3974–3975. doi:10.1021/ja00036a053.
  8. ↑ Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. "A Series of Well-Defined Metathesis Catalysts – Synthesis of [RuCl2(=CHR′)(PR3)2] and Its Reactions". Angew. Chem. Int. Ed. 34 (18): 2039–2041. doi:10.1002/anie.199520391.
  9. ↑ Schwab, P.; Grubbs, R. H.; Ziller, J. W. (1996). "Synthesis and Applications of RuCl2(=CHR′)(PR3)2: The Influence of the Alkylidene Moiety on Metathesis Activity". J. Am. Chem. Soc. 118 (1): 100–110. doi:10.1021/ja952676d.
  10. ↑ Huang, J.-K.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. (1999). "Olefin Metathesis-Active Ruthenium Complexes Bearing a Nucleophilic Carbene Ligand". J. Am. Chem. Soc. 121 (12): 2674–2678. doi:10.1021/ja9831352.
  11. ↑ Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. (1999). "Increased Ring Closing Metathesis Activity of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with Imidazolin-2-ylidene Ligands". Tetrahedron Lett. 40 (12): 2247–2250. doi:10.1016/S0040-4039(99)00217-8.
  12. ↑ Ackermann, L.; Fürstner, A.; Weskamp, T.; Kohl, F. J.; Herrmann, W. A. (1999). "Ruthenium Carbene Complexes with Imidazolin-2-ylidene Ligands Allow the Formation of Tetrasubstituted Cycloalkenes by RCM". Tetrahedron Lett. 40 (26). doi:10.1016/S0040-4039(99)00919-3.
  13. ↑ Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. (1999). "Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene Ligands". Org. Lett. 1 (6): 953–956. doi:10.1021/ol990909q.
  14. ↑ Kingsbury, Jason S.; Harrity, Joseph P. A.; Bonitatebus, Peter J.; Hoveyda, Amir H. (1999). "A Recyclable Ru-Based Metathesis Catalyst". J. Am. Chem. Soc. 121 (4): 791–799. doi:10.1021/ja983222u.
  15. 1 2 Gessler, S.; Randl, S.; Blechert, S. (2000). "Synthesis and metathesis reactions of phosphine-free dihydroimidazole carbene ruthenium complex". Tetrahedron Letters. 41 (51): 9973–9976. doi:10.1016/S0040-4039(00)01808-6.
  16. 1 2 Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. (2000). "Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts". J. Am. Chem. Soc. 122 (34): 8168–8179. doi:10.1021/ja001179g.
  17. ↑ Engle, Keary M.; Lu, Gang; Luo, Shao-Xiong; Henling, Lawrence M.; Takase, Michael K.; Liu, Peng; Houk, K. N.; Grubbs, Robert H. (2015). "Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes". Journal of the American Chemical Society. 137 (17): 5782–5792. doi:10.1021/jacs.5b01144.
  18. ↑ Hong, Soon Hyeok; Grubbs, Robert H. (2006). "Highly Active Water-Soluble Olefin Metathesis Catalyst". J. Am. Chem. Soc. 128 (11): 3508–3509. doi:10.1021/ja058451c. PMID 16536510.
  19. ↑ Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. (2002). "A Practical and Highly Active Ruthenium-Based Catalyst that Effects the Cross Metathesis of Acrylonitrile". Angew. Chem. Int. Ed. Engl. 41 (21): 4035–4037. doi:10.1002/1521-3773(20021104)41:21<4035::AID-ANIE4035>3.0.CO;2-I.
  20. ↑ Walsh, Dylan J.; Lau, Sii Hong; Hyatt, Michael G.; Guironnet, Damien (2017-09-25). "Kinetic Study of Living Ring-Opening Metathesis Polymerization with Third-Generation Grubbs Catalysts". Journal of the American Chemical Society. 139 (39): 13644–13647. doi:10.1021/jacs.7b08010. ISSN 0002-7863.
  21. ↑ Leitgeb, Anita; Wappel, Julia; Slugovc, Christian (2010). "The ROMP toolbox upgraded". Polymer. 51 (14): 2927–2946. doi:10.1016/j.polymer.2010.05.002.
  22. ↑ Choi, T.-L.; Grubbs, R. H. (2003). "Controlled Living Ring-Opening-Metathesis Polymerization by a Fast-Initiating Ruthenium Catalyst". Angewandte Chemie International Edition. 42 (15): 1743–1746. doi:10.1002/anie.200250632.
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