Photoactivation of Ruthenium Phosphite Complexes for Olefin Metathesis

Eivgi, Or; Guidone, Stefano; Frenklah, Alexander; Kozuch, Sebastian; Goldberg, Israel; Lemcoff, N. Gabriel

doi:10.1021/acscatal.8b01637

Cited by 31 publications

(43 citation statements)

References 45 publications

(20 reference statements)

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“…The catalyst provided excellent results for both options, the activation, and the self-destruction; however, a major drawback of this catalyst was the lengthy and difficult synthesis of the NHC ligand and its installation on the ruthenium complex. Recently, we discovered that latent metathesis catalysts-bearing phosphite ligands, for example, the commercially available catalyst cis-Caz-1, may be efficiently activated with UV-A and even visible light [56]. This discovery led to the design of novel phosphite containing latent metathesis catalysts.…”

Section: Development Of the Methodsmentioning

confidence: 99%

Sunscreen-Assisted Selective Photochemical Transformations

Eivgi

Lemcoff

2020

Molecules

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In this review, we describe a simple and general procedure to accomplish selective photochemical reaction sequences for two chromophores that are responsive to similar light frequencies. The essence of the method is based on the exploitation of differences in the molar absorptivity at certain wavelengths of the photosensitive groups, which is enhanced by utilizing light-absorbing auxiliary filter molecules, or “sunscreens”. Thus, the filter molecule hinders the reaction pathway of the least absorbing molecule or group, allowing for the selective reaction of the other. The method was applied to various photochemical reactions, from photolabile protecting group removal to catalytic photoinduced olefin metathesis in different wavelengths and using different sunscreen molecules. Additionally, the sunscreens were shown to be effective also when applied externally to the reaction mixture, avoiding any potential chemical interactions between sunscreen and substrates and circumventing the need to remove the light-filtering molecules from the reaction mixture, adding to the simplicity and generality of the method.

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Section: Development Of the Methodsmentioning

confidence: 99%

Sunscreen-Assisted Selective Photochemical Transformations

Eivgi

Lemcoff

2020

Molecules

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“… 2018 8 6413 6418 . 3 Discovery of the photoactivation feature of the commercially available ruthenium phosphite complex cis- Caz-1 , making photoinduced olefin metathesis widely accessible. Latent Ruthenium Benzylidene Phosphite Complexes for Visible Light Induced Olefin Metathesis Eivgi O.…”

Section: Key Referencesmentioning

confidence: 99%

Section: Key Referencesmentioning

confidence: 99%

“…Indeed, cis - Caz-1 was found to be readily activated under UV-A light (350 nm), becoming the first (and to date only) commercially available photoswitchable metathesis catalyst, making photoinduced olefin metathesis widely accessible. 3 The light-induced catalytic activity of cis - Caz-1 was thoroughly studied and showed great competence for a variety of ROMP, RCM, and CM reactions ( Figure 14 a). The study of ROMP of 1,5-cyclooctadiene (COD) using cis - Caz-1 disclosed an intriguing solvent effect ( Figure 14 b).…”

Section: Photoactivation Of Ruthenium Phosphite Complexes For Olefin mentioning

confidence: 99%

“…Thus, 42 was synthesized and reacted with the Hoveyda–Grubbs second-generation catalyst to afford complex 43 - cis ( Scheme 14 ). 3 …”

Section: Photoactivation Of Ruthenium Phosphite Complexes For Olefin mentioning

confidence: 99%

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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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Emerging Trends in Ring‐opening Metathesis Polymerization

Cao¹,

Pichavant²,

Trinh³

et al. 2022

Macromolecular Engineering

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This article presents the different techniques and strategies that have been explored over the last decade to overcome synthetic challenges and produce a wide range of new (nano)materials by ring‐opening metathesis polymerization (ROMP). In a first part, recent developments in photochemically activated ROMP are critically discussed. The second part is devoted to the synthesis of nanoparticles in dispersed media and by self‐assembly. The last two parts are dedicated to two interesting ROMP developments, the first in the medical field and the last part on different separation techniques.

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Photoactivation of Ruthenium Phosphite Complexes for Olefin Metathesis

Cited by 31 publications

References 45 publications

Sunscreen-Assisted Selective Photochemical Transformations

Sunscreen-Assisted Selective Photochemical Transformations

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

Emerging Trends in Ring‐opening Metathesis Polymerization

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