Cross Metathesis

The transalkylidenation of two terminal alkenes under release of ethene, catalyzed by ruthenium carbenoids (Grubbs Catalyst). Statistically, the reaction can lead to three possible pairs of geometric isomers, i.e. E/Z pairs for two homocouplings and the cross-coupling (R-CH=CH-R, R'-CH=CH-R', and R-CH=CH-R') - a total of 6 products.

The selectivity of this reaction is currently undergoing further study, but various examples exist in which two alkenes with different reactivity give the cross-coupled product with excellent yields and excellent selectivity.

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Mechanism of Cross Metathesis

See Olefin Metathesis

Recent Literature

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.

Rate Enhanced Olefin Cross-Metathesis Reactions: The Copper Iodide Effect
K. Voigtritter, S. Ghorai, B. H. Lipshutz, J. Org. Chem., 2011, 76, 4697-4702.

Olefin Cross-Metathesis Reactions at Room Temperature Using the Nonionic Amphiphile “PTS”: Just Add Water
B. H. Lipshutz, G. T. Aquinaldo, S. Ghorai, K. Voigtritter, Org. Lett., 2008, 10, 1325-1328.

Increased Efficiency in Cross-Metathesis Reactions of Sterically Hindered Olefins
I. C. Stewart, C. J. Douglas, R. H. Grubbs, Org. Lett., 2008, 10, 441-444.

Merging Grubbs second-generation catalyst with photocatalysis enables Z-selective metathesis of olefins: scope, limitations, and mechanism
S. E. Chérif, A. Ghosh, S. Chelli, I. M. Dixon, J. Kraiem, S. Lakhdar, J. Org. Chem., 2022, 87, 12065-12070.

Stereoretentive Olefin Metathesis Made Easy: In Situ Generation of Highly Selective Ruthenium Catalysts from Commercial Starting Materials
D. S. Müller, I. Curbet, Y. Raoul, J. Le Nôtre, O. Baslé, M. Mauduit, Org. Lett., 2018, 20, 6822-6826.

Synthesis of Z- or E-Trisubstituted Allylic Alcohols and Ethers by Kinetically Controlled Cross-Metathesis with a Ru Catechothiolate Complex
C. Xu, Z. Liu, S. Torker, X. Shen, D. Xu, A. H. Hoveyda, J. Am. Chem. Soc., 2017, 139, 15640-15643.

Acryloyl Chloride: An Excellent Substrate for Cross-Metathesis. A One-Pot Sequence for the Synthesis of Substituted α,β-Unsaturated Carbonyl Derivatives
L. Ferrié, S. Bouzbouz, J. Cossy, Org. Lett., 2009, 11, 5446-5448.

A Rapid and Simple Cleanup Procedure for Metathesis Reactions
B. R. Galan, K. P. Kalbarczyk, S. Szczepankiewicz, J. B. Keister, S. T. Diver, Org. Lett., 2007, 9, 1203-1206.

Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis
M. J. Koh, T. T. Ngyuen, H. Zhang, R. R. Schrock, A. H. Hoveyda, Nature, 2016, 531, 459-465.

Regioselective Cross-Metathesis Reaction Induced by Steric Hindrance
S. BouzBouz, R. Simmons, J. Cossy, Org. Lett., 2004, 6, 3465-3467.

An Efficient Synthesis of Nitroalkenes by Alkene Cross Metathesis: Facile Access to Small Ring Systems
G. P. Marsh, P. J. Parsons, C. McCarthy, X. G. Corniquet, Org. Lett., 2007, 9, 2613-2616.

Selective Synthesis of (2Z,4E)-Dienyl Esters by Ene-Diene Cross Metathesis
G. Moura-Letts, D. P. Curran, Org. Lett., 2007, 9, 5-8.

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.

A Good Bargain: An Inexpensive, Air-Stable Ruthenium Metathesis Catalyst Derived from α-Asarone
K. Grela, M. Kim, Eur. J. Org. Chem., 2003, 963-966.

The facile preparation of alkenyl metathesis synthons
T. W. Baughman, J. C. Sworen, K. B. Wagener, Tetrahedron, 2004, 60, 10943-10948.

Ruthenium-Catalyzed Tandem Olefin Metathesis-Oxidations
A. A. Scholte, M. H. An, M. L. Snapper, Org. Lett., 2006, 8, 4759-4762.

Ruthenium-Catalyzed Tandem Cross-Metathesis/Wittig Olefination: Generation of Conjugated Dienoic Esters from Terminal Olefins
R. P. Murelli, M. L. Snapper, Org. Lett., 2007, 9, 1749-1752.

Preparation of Aliphatic Ketones through a Ruthenium-Catalyzed Tandem Cross-Metathesis/Allylic Alcohol Isomerization
D. Finnegan, B. A. Seigal, M. L. Snapper, Org. Lett., 2006, 8, 2603-2606.

Heteroaromatic Synthesis via Olefin Cross-Metathesis: Entry to Polysubstituted Pyridines
T. J. Donohoe, J. A. Basutto, J. F. Bower, A. Rathi, Org. Lett., 2011, 13, 1036-1039.

Cross Metathesis of N-Allylamines and α,β-Unsaturated Carbonyl Compounds: A One-Pot Synthesis of Substituted Pyrroles
S. Shafi, M. Kędziorek, K. Grela, Synlett, 2011, 124-128.

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Selected Articles

The Grubbs Reaction in Organic Synthesis
Enantioselective Total Synthesis of (+)-Amphidinolide T1