Olefin metathesis catalyst bearing a chelating phosphine ligand

Lexer, Christina; Burtscher, Daniel; Perner, Bernhard; Tzur, Eyal; Lemcoff, N. Gabriel; Slugovc, Christian

doi:10.1016/j.jorganchem.2011.03.005

Cited by 38 publications

(24 citation statements)

References 31 publications

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“…The resulting distributions of substrate DEDAM and the products 5a, 5b, and 5c were compared. NMR spectroscopic data of the products are identical to those published previously [37].…”

Section: Rcm Experimentssupporting

confidence: 66%

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

2012

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Upon comparative NMR spectroscopy studies, the isomerization of newly disclosed dichloro [j 2 (C,O)-2-(N-propylaminocarbonyl)benzylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium from trans-dichloro configuration (SPY-5-31) to its thermodynamically more favored cis-dichloro derivative (with SPY-5-34 stereochemistry) was found to proceed via dissociation of one chloride ligand to form an intermediate cationic species. Furthermore, the performance of the trans-and the cis-dichloro derivatives as catalysts in ringclosing metathesis and as initiators in ring-opening metathesis polymerization was studied.

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“…The resulting distributions of substrate DEDAM and the products 5a, 5b, and 5c were compared. NMR spectroscopic data of the products are identical to those published previously [37].…”

Section: Rcm Experimentssupporting

confidence: 66%

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

2012

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“…42 Ligands with a strongly coordinating heteroatom chelator such as oxygen, 43 nitrogen, 44 sulfur, 45 and selenium 46 provide greater thermal stability. For instance, Slugovc and co-workers 47 began exploring the use of ruthenium alkylidene catalysts bearing a chelating phosphine ligand Ru-V for both ring-opening metathesis polymerization and ring-closing metathesis (Scheme 8). When this catalyst was used for the synthesis of pyrroline 33, it provided the desired product in >97% yield with reaction temperatures as high as 110 °C.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

“…Scheme 8 Role of chelating ligands, solvents and additives in ring closing metathesis 47,49 While the phosphine chelator provides increased stability of the active methylidene species at elevated temperatures, another continued goal is accessing a tunable, shelfstable catalyst. Such a catalyst was serendipitously discovered by Williams, Kong and co-workers in 2016 during the synthesis of the macrocyclic backbone of the HCV therapeutic agent grazoprevir 48 (MK-5172, 37) from 38 via ringclosing metathesis using HG-II (Scheme 9); 49 the first quinoxaline Ru-VI (Scheme 8) was isolated as a byproduct of the metathesis reaction.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Recent Advances in the Application of Ring-Closing Metathesis for the Synthesis of Unsaturated Nitrogen Heterocycles

Groso

Schindler

2019

Synthesis

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This short review summarizes recent advances relating to the application of ring-closing olefin-olefin and carbonyl-olefin metathesis reactions towards the synthesis of unsaturated five- and six-membered nitrogen heterocycles. These developments include catalyst modifications and reaction designs that will enable access to more complex nitrogen heterocycles.1 Introduction2 Expansion of Ring-Closing Metathesis Methods3 Evaluation of Catalyst Design4 Indenylidene Catalysts5 Unsymmetrical N-Heterocyclic Carbene Ligands6 Carbonyl-Olefin Metathesis7 Conclusions

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“… 56 As expected, these catalysts were metathesis-active at ambient temperatures. On the basis of a previous study on chelating phosphine ligands, 57 we surmised that a chelating benzylidene phosphite ligand would force a cis -dichloro configuration. Thus, 42 was synthesized and reacted with the Hoveyda–Grubbs second-generation catalyst to afford complex 43 - cis ( Scheme 14 ).…”

Section: Photoactivation Of Ruthenium Phosphite Complexes For Olefin mentioning

confidence: 99%

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

et al. 2020

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Conspectus The most important means for tuning and improving a catalyst’s properties is the delicate exchange of the ligand shell around the central metal atom. Perhaps for no other organometallic-catalyzed reaction is this statement more valid than for ruthenium-based olefin metathesis. Indeed, even the simple exchange of an oxygen atom for a sulfur atom in a chelated ruthenium benzylidene about a decade ago resulted in the development of extremely stable, photoactive catalysts. This Account presents our perspective on the development of dormant olefin metathesis catalysts that can be activated by external stimuli and, more specifically, the use of light as an attractive inducing agent. The insight gained from a deeper understanding of the properties of cis -dichlororuthenium benzylidenes opened the doorway for the systematic development of new and efficient light-activated olefin metathesis catalysts and catalytic chromatic-orthogonal synthetic schemes. Following this, ways to disrupt the ligand-to-metal bond to accelerate the isomerization process that produced the active precatalyst were actively pursued. Thus, we summarize herein the original thermal activation experiments and how they brought about the discoveries of photoactivation in the sulfur-chelated benzylidene family of catalysts. The specific wavelengths of light that were used to dissociate the sulfur–ruthenium bond allowed us to develop noncommutative catalytic chromatic-orthogonal processes and to combine other photochemical reactions with photoinduced olefin metathesis, including using external light-absorbing molecules as “sunscreens” to achieve novel selectivities. Alteration of the ligand sphere, including modifications of the N-heterocyclic carbene (NHC) ligand and the introduction of cyclic alkyl amino carbene (CAAC) ligands, produced more efficient light-induced activity and special chemical selectivity. The use of electron-rich sulfoxides and, more prominently, phosphites as the agents that induce latency widened the spectrum of light-induced olefin metathesis reactions even further by expanding the colors of light that may now be used to activate the catalysts, which can be used in applications such as stereolithography and 3D printing of tough metathesis-derived polymers.

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Olefin metathesis catalyst bearing a chelating phosphine ligand

Cited by 38 publications

References 31 publications

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

Recent Advances in the Application of Ring-Closing Metathesis for the Synthesis of Unsaturated Nitrogen Heterocycles

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

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