Deactivation of Ruthenium Olefin Metathesis Catalysts through Intramolecular Carbene–Arene Bond Formation

Abstract

Dedicated to Professor Ekkehard Winterfeldt on the occasion of his 75th birthdaySince the development of Grubbs catalysts of the first ([RuCl 2 (PCy 3 ) 2 (=CHÀC 6 H 5 )] (1; Cy= cyclohexyl) and second (2) generation, many modified ruthenium complexes for olefin metathesis have been reported, [1] for which strikingly different influences of the ligands on the efficiency of CÀC bond formation have been observed. For example, notable effects have been found in the class of alkoxy benzylidene ligands first introduced by Hoveyda and coworkers. Phosphine-free complexes such as the secondgeneration Hoveyda-Grubbs catalyst (4; IMesH 2 = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [2] are especially wellsuited for cross metathesis with electron-deficient olefins such as a,b-unsaturated nitriles.[3] The stability and the initiation rate of the precatalyst could be tuned by steric and electronic effects of the substituents. [4] Additional intramolecular interactions of functional groups or atoms with the metal center have been reported for some ligands. [3c, 5, 6] Grubbs and co-workers recently found an accelerating effect in olefin metathesis through fluorineruthenium interaction. Besides knowledge of such ligand and substituent effects, an understanding of catalyst decomposition and transformation to catalytically inactive ruthenium species is of major importance for the rational design and improvement of metathesis catalysts. Fundamental studies have been presented by Grubbs and co-workers and by Dinger and Mol.[7] Herein, we report a novel deactivation reaction pathway transforming active ruthenium catalysts with alkoxy benzylidene ligands into catalytically inactive carbene complexes.During our study of diastereoselective ring rearrangement metathesis reactions (dRRM), we found that the neutral ligand that remains on the metal center has a pronounced effect on conversion and diastereoselectivity.[8] While only moderate diastereoselectivities could be seen for the firstgeneration catalysts (1, 3), the sterically more demanding and more active second-generation catalysts (2, 4) led to significantly higher selectivities. Thus, we focused on the development of a bulky ruthenium carbene complex to increase the diastereoselective interaction between the olefine moiety and the catalytically active ruthenium species. To do this, we connected the N-aryl substituent with the N-heterocyclic carbene (NHC) through a C 2 unit. Unlike in 2 or 4, the aromatic moiety in this new ruthenium complex (5, Scheme 1) should exert a much stronger steric influence on the ruthenium alkylidene moiety through torsion of approximately 458 and hindered rotation.The synthesis of the NHC ligand started from commercially available 2,2'-biquinoline (6). The first step was hydration to octahydrobiquinoline; the result of the hydration was strongly dependent on the catalyst system. PtO 2 and H 2 under ambient pressure led to the formation of a 3:1 mixture of the meso and racemic forms. Simple chromatography on silica gel Scheme 1. Synthesis of ruthe...

NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

“…In the ring-closing metathesis of N,N-diallyl-4-methylbenzenesulfonamide, complex 5-synHGII was slightly less active than the benchmark catalysts HGIItol, especially at low catalyst loadings. In 2007 Blechert and coworkers presented a new ruthenium complex 6-synGII ( Figure 5) containing an NHC ligand in which the N-aryl substituents were connected to the NHC backbone through a syn related C2 unit [37]. In this complex, the steric influence exerted by the aromatic moiety on the ruthenium alkylidene moiety is much stronger than in GII, therefore an increase of the diastereoselectivity of ring rearrangement metathesis reactions (dRRM) was expected.…”

“…The synthesis of 7-synGII and 7-antiGII proceeded in good yield (55%-60%), although it required several steps, including the preparation of meso and chiral 1,2-diamines [38] to achieve the corresponding NHC ligand precursors. In 2007 Blechert and coworkers presented a new ruthenium complex 6-synGII ( Figure 5) containing an NHC ligand in which the N-aryl substituents were connected to the NHC backbone through a syn related C2 unit [37]. In this complex, the steric influence exerted by the aromatic moiety on the ruthenium alkylidene moiety is much stronger than in GII, therefore an increase of the diastereoselectivity of ring rearrangement metathesis reactions (dRRM) was expected.…”

Deactivation of Ru-benzylidene Grubbs catalysts active in olefin metathesis

“…However, one of the drawbacks slowing this step still is the scarce stability of otherwise quite active N-heterocyclic carbene (NHC)-based second-generation catalysts [2][3][4][5]. The greater activity of NHC-based catalysts is now rather well understood [3,[6][7][8][9][10], while knowledge about their stability is still scarce [11][12][13][14][15][16].…”

Ein neuer Ligand für die Ruthenium‐katalysierte enantioselektive Olefinmetathese

“…Kristallstruktur von 3 b aus zwei Perspektiven. [13] Tabelle 1: Test der Katalysatoren in der AROCM mit Styrol als Kreuzmetathesepartner. [a] Nr.…”