From Environmentally Friendly Reusable Ionic-Tagged Ruthenium-Based Complexes to Industrially Relevant Homogeneous Catalysts: Toward a Sustainable Olefin Metathesis

Abstract

International audienceThis account describes our investigations, over the past decade, on the design of ruthenium-based complexes dedicated to sustainable olefin metathesis. An overview of different classes of catalysts, from reusable ionically tagged systems to industrially relevant homogeneous complexes, including latent catalysts, is disclosed. Challenging applications involving these robust complexes, including the valorization of olefin feedstock derived from biomass into valuable building blocks, are also discussed. 1 Introduction 2 Reusable Ionically Tagged Ruthenium Complexes for Olefin Metathesis in RTILs and Related SILP Processes 2.1 The First Generation: Olefin Metathesis in [BMIM]PF6 2.2 The Second Generation: Olefin Metathesis in Biphasic [BMIM]PF6/ ­Toluene Medium 2.3 Initiation Rates Versus Recyclability: The Linker Choice 2.4 Modulation of the NHC Unit: Toward the Optimum Reusable Catalytic System 2.5 Introduction of Aminocarbonyl-Based Linkers 2.6 The SILP Technology: Toward Olefin Metathesis in Continuous Flow 2.7 Catalysts Bearing an Ionically Tagged NHC Ligand 3 Structural Modifications Around the Styrenyl Ether Ligand for the Control of Initiation Rates: Toward a Library of Industrially Relevant Homogeneous Hoveyda-Type Complexes 3.1 Aminocarbonyl-Functionalized Complexes (M7) 3.1.1 Industrial-Scale Production of Complexes M71-SIPr and M73-SIPr 3.2 Aminosulfonyl-Tagged Ruthenium Complexes 3.3 Oxazine- and Oxazinone-Functionalized Ruthenium Complexes 3.4 Synthetic Applications 3.4.1 Production of High Added-Value Molecules 3.4.2 Valorization of Bio-Sourced Molecules 4 Ruthenium Complexes Bearing Unsymmetrical Cycloalkyl-NHCs: Efficient and Selective Catalysts for the Metathesis of α-Olefins 4.1 A Low-Cost Synthetic Route: The Arduengo Process Revisited Providing Unsymmetrical Unsaturated (U2)-NHCs and their Corresponding Ruthenium Complexes 4.2 Application in the Selective Metathesis of α-Olefins from Bio-Sourced Fischer-Tropsch Feeds 5 Design of Latent Ruthenium Complexes 5.1 A 'Dormant' Catalyst Bearing a Chelating Carboxylate Ligand 5.2 Ruthenium-Indenylidene Catalysts Bearing a Bidentate Picolinate Ligand 5.3 Serendipitous Discovery of Cationic Bis-NHC Hoveyda-Type Complexes 6 Conclusions and Outlook. © Georg Thieme Verlag Stuttgart · New York

Activated Hoveyda‐Grubbs Olefin Metathesis Catalysts Derived from a Large Scale Produced Pharmaceutical Intermediate – Sildenafil Aldehyde

“…[9] Subsequently, the introduction of electron withdrawing group (EWG) in the chelating benzylidene moiety of Hoveyda-Grubbs type complexes led to a further increase of the activity and stability of such obtained catalysts enabling the decrease of the catalyst loading concomitantly with an increase in application scope. [10] In this regard, Grela, [11] Zhan, [12] and Mauduit [13] developed several activated derivatives of Hov-II, that were substituted in the chelating benzylidene fragment with electron withdrawing groups such as NO 2 (Gre), SO 2 NMe 2 (Zha), and NHC(O)CF 3 (Mau; Figure 1). Despite their usually higher activity and some promising applications, [14] the synthesis of such catalysts require more synthetic steps as compared to the parental unsubstituted Hov-II complex.…”

MOF Encapsulation of Ru Olefin Metathesis Catalysts to Block Catalyst Decomposition

“…To improve the performance of olefin metathesis catalysts, attempts to anchor them by means of their ionization led to ammonium-tagged Ru-alkylidene metathesis catalysts [17][18][19]. This represents the addition of the Brönsted acid nature in the framework of olefin metathesis [20][21][22].…”

Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules

“…Alkene and alkyne metathesis [1][2][3][4], constituting highly versatile and powerful catalytic processes for constructing complex organic molecules [5][6][7][8][9][10][11][12], have found broad application in the fields of pharmaceutical synthesis [13][14][15], materials science [16][17][18][19][20], or in advanced techniques and technologies [21][22][23][24][25][26][27][28][29][30]. Thus, numerous multistep total syntheses of organic compounds, including bioactive molecules [31][32][33][34][35] and natural products [36,37], have been performed in a highly chemo-and stereoselective manner through metathesis routes [38][39][40][41][42][43].…”