Ring Closing Metathesis (RCM)

The Ring-Closing Metathesis (RCM) allows synthesis of 5- up to 30-membered cyclic alkenes. The E/Z-selectivity depends on the ring strain.

The Ru-catalysts used tolerate a variety of functional groups, but normally the molecule must have polar side chains that are able to build a template for the catalyst. The modern Second Generation Grubb's Catalysts (see Olefin Metathesis) are more versatile.

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Mechanism of Ring Closing Metathesis

The key intermediate is a metallacyclobutane, which can undergo cycloreversion either towards products or back to starting materials. When the olefins of the substrate are terminal, the driving force for RCM is the removal of ethene from the reaction mixture.

Initiation:

Catalytic cycle:

Chauvin's Mechanism

Recent Literature

Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene Ligands
M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett., 1999, 1, 953-956.

Synthesis of 1,2-Disubstituted Cyclopentadienes from Alkynes Using a Catalytic Haloallylation/Cross-Coupling/Metathesis Relay
N. Topolovčan, I. Panov, Martin Kotora, Org. Lett., 2016, 18, 3634-3637.

A Selective and Functional Group-Tolerant Ruthenium-Catalyzed Olefin Metathesis/Transfer Hydrogenation Tandem Sequence Using Formic Acid as Hydrogen Source
G. K. Zieliński, J. Majtczak, M. Gutowski, K. Grela, J. Org. Chem., 2018, 83, 2542-2553.

A Convenient Method for the Efficient Removal of Ruthenium Byproducts Generated during Olefin Metathesis Reactions
Y. M. Ahn, K. Yang, G. I. Georg, Org. Lett., 2001, 3, 1411-1413.

Indenylidene Ruthenium Complex Bearing a Sterically Demanding NHC Ligand: An Efficient Catalyst for Olefin Metathesis at Room Temperature
H. Clavier, C. A. Urbino-Blanco, S. P. Nolan, Organometallics, 2009, 28, 2848-2854.

Aminocarbonyl Group Containing Hoveyda-Grubbs-Type Complexes: Synthesis and Activity in Olefin Metathesis Transformations
D. Rix, F. Caijo, I. Laurent, F. Boeda, H. Clavier, S. P. Nolan, M. Mauduit, J. Org. Chem., 2008, 73, 4225-4228.

Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis
C. Theunissen, M. A. Ashley, T. Rovis, J. Am. Chem. Soc., 2019, 141, 6791-6796.

Synthesis of Functionalized Olefins by Cross and Ring-Closing Metatheses
A. K. Chatterjee, J. P. Morgan, M. Scholl, R. H. Grubbs, J. Am. Chem. Soc., 2000, 122, 3783-3784.

Enamide-Olefin Ring-Closing Metathesis
S. S. Kinderman, J. H. van Maarseveen, H. E. Schoemaker, H. Hiemstra, F. P. J. T. Rutjes, Org. Lett., 2001, 3, 2077-2079.

Pd, Ru, and Fe catalysis enable a general synthesis of 2-substituted pyrroles in overall good yields with only water and ethene as side-products. The route starts with two subsequent Pd-catalyzed monoallylations of amines with allylic alcohols. Ru-catalyzed ring-closing metathesis performed on the diallylated amines provides pyrrolines in excellent yields. By addition of ferric chloride, a selective aromatization was achieved.
A. Bunrit, S. Sawadjoon, S. Tšupova, P. J. R. Sjöberg, J. S. M. Samec, J. Org. Chem., 2016, 81, 1450-1460.

Supported Ruthenium-Carbene Catalyst on Ionic Magnetic Nanoparticles for Olefin Metathesis
S.-W. Chen, Z.-C. Zhang, M. Ma, C.-M. Zhong, S.-g. Lee, Org. Lett., 2014, 16, 4969-4971.

Synthesis of Imidazolium-Tagged Ruthenium Carbene Complex: Remarkable Activity and Reusability in Regard to Olefin Metathesis in Ionic Liquids
H. Wakamatsu, Y. Saito, M. Masubuchi, R. Fujita, Synlett, 2008, 1805-1808.

Allenylidene-to-Indenylidene Rearrangement in Arene-Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions
R. Castarlenas, C. Vovard, C. Fischmeister, P. H. Dixneuf, J. Am. Chem. Soc., 2006, 128, 4079-4089.

Advanced Fine-Tuning of Grubbs/Hoveyda Olefin Metathesis Catalysts: A Further Step toward an Optimum Balance between Antinomic Properties
M. Bieniek, R. Bujok, M. Cabaj, N. Lugan, G. Lavigne, D. Arlt, K. Grela, J. Am. Chem. Soc., 2006, 128, 13652-13653.

PQS: A New Platform for Micellar Catalysis. RCM Reactions in Water, with Catalyst Recycling
B. H. Lipshutz, S. Ghorai, Org. Lett., 2009, 11, 705-708.

Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst
V. Polshettiwar, R. S. Varma, J. Org. Chem., 2008, 73, 7417-7419.

N-Sulfonyl- and N-acylpyrroles were synthesized via olefin ring-closing metathesis of diallylamines followed by in situ oxidative aromatization in the presence of the ruthenium Grubbs catalyst and a suitable copper catalyst. Under an oxygen atmosphere, the reaction worked smoothly without the need of hydroperoxide oxidants.
W. Chen, Y.-L. Zhang, H.-J. Li, X. Nan, Y. Liu, Y.-C. Wu, Synthesis, 2019, 51, 3651-3666.

Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts
S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc., 2000, 122, 8168-8179.

Δ³-Aryl/heteroaryl substituted heterocycles via sequential Pd-catalysed termolecular cascade/ring closing metathesis (RCM)
H. A. Dondas, B. Clique, B. Cetinkaya, R. Grigg, C. Kilner, J. Morris, V. Sridharan, Tetrahedron, 2005, 61, 10652-10666.

Synthesis of Nitrogen-Containing Heterocycles via Ring-Closing Ene-Ene and Ene-Yne Metathesis Reactions: An Easy Access to 1- and 2-Benzazepine Scaffolds and Five- and Six-Membered Lactams
E. Benedetti, M. Lomazzi, F. Tibiletti, J.-P. Goddard, L. Fensterbank, M. Malacria, G. Palmisano, A. Penoni, Synthesis, 2012, 44, 3523-3533.

Synthesis of Sultams by Ring-Closing Metathesis
S. Mondal, S. Debnath, Synthesis, 2014, 46, 368-374.

Studies on the Synthesis of Endocyclic Enol Lactones via a RCM of Selected Vinyl Esters
A. Brodzka, F. Borys, D. Koszelewski, R. Ostaszewski, J. Org. Chem., 2018, 83, 8655-8661.

Synthesis of Fused Bicyclic Imidazoles by Sequential Van Leusen/Ring-Closing Metathesis Reactions
V. Gracias, A. F. Gasiecki, S. W. Djuric, Org. Lett., 2005, 7, 3183-3186.

Enantioselective Synthesis of Cyclic Amides and Amines through Mo-Catalyzed Asymmetric Ring-Closing Metathesis
E. S. Sattely, G. Alexander Cortez, D. C. Moebius, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc., 2005, 127, 8526-8533.

An Efficient Route to Benzene and Phenol Derivatives via Ring-Closing Olefin Metathesis
K. Yoshida, S. Horiuchi, N. Iwadate, F. Kawagoe, T. Imamoto, Synlett, 2007, 1561-1562.

A New Synthetic Approach to Phenol Derivatives: Use of Ring-Closing Olefin Metathesis
K. Yoshida, T. Imamoto, J. Am. Chem. Soc., 2005, 127, 10470-10471.

An isomerization-ring-closing metathesis strategy for the synthesis of substituted benzofurans
W. A. L. van Otterlo, G. L. Morgans, L. G. Madeley, S. Kuzvidza, S. S. Moleele, N. Thornton, C. B. de Koning, Tetrahedron, 2005, 61, 7746-7755.

Synthesis of α,β-Unsaturated 4,5-Disubstituted γ-Lactones via Ring-Closing Metathesis Catalyzed by the First-Generation Grubbs' Catalyst
M. Bassetti, A. D'Annibale, A. Fanfoni, F. Minissi, Org. Lett., 2005, 7, 1805-1808.

An Olefin Metathesis/Double Bond Isomerization Sequence Catalyzed by an In Situ Generated Ruthenium Hydride Species
B. Schmidt, Eur. J. Org. Chem., 2003, 816-819.

Imino Glycals via Ruthenium-Catalyzed RCM and Isomerization
B. Schmidt, S. Hauke, N. Mühlenberg, Synthesis, 2014, 46, 1648-1658.

Multicatalytic Processes Using Diverse Transition Metals for the Synthesis of Alkenes
H. Lebel, V. Paquet, J. Am. Chem. Soc., 2004, 126, 11152-11153.

Highly Active Ruthenium Metathesis Catalysts Exhibiting Unprecedented Activity and Z-Selectivity
L. E. Rosebrugh, M. B. Herbert, V. M. Marx, B. K. Keitz, R. H. Grubbs, J. Am. Chem. Soc., 2013, 135, 1276-1279.

Chelate-Assisted Ring-Closing Metathesis: A Strategy for Accelerating Macrocyclization at Ambient Temperatures
C. S. Higman, D. L. Nascimento, B. J. Ireland, S. Audörsch, G. A. Bailey, R. McDonald, D. E. Fogg, J. Am. Chem. Soc., 2018, 140, 1604-1607.

Synthesis of Selectively Substituted or Deuterated Indenes via Sequential Pd and Ru Catalysis
A. Jana, K. Misztal, A. Żak, K. Grela, J. Org. Chem., 2017, 82, 4226-4234.

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Selected Articles

N-Heterocycle Construction by Alkene Metathesis
The Grubbs Reaction in Organic Synthesis
Synthesis of (+)-4,5-Deoxyneodolabelline