Further Information
Literature
Related Reactions
Cross Metathesis
Enyne Metathesis
Olefin Metathesis
Ring Opening Metathesis
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.
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.
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.
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.
Selected Articles
N-Heterocycle Construction by
Alkene Metathesis
The Grubbs Reaction in Organic Synthesis
Synthesis of (+)-4,5-Deoxyneodolabelline