Roll-over cyclometalation: A versatile tool to enhance the catalytic activity of transition metal complexes

Leist, Marko; Kerner, Christian; Ghoochany, Leila Taghizadeh; Farsadpour, Saeid; Fizia, Agnes; Neu, Jens; Schön, Florian; Sun, Yu; Oelkers, Benjamin; Lang, Johannes; Menges, Fabian; Niedner‐Schatteburg, Gereon; Salih, Kifah S. M.; Thiel, Werner R.

doi:10.1016/j.jorganchem.2018.03.022

Cited by 27 publications

(31 citation statements)

References 94 publications

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“…A proposed catalytic cycle ( Figure 68 ), involving hydrogen transfer reactions, rollover and retro-rollover reactions, was supported by NMR spectroscopy, kinetic studies, IR-MPD, ESI-MS, and DFT calculations [ 18 , 71 , 72 , 126 ].…”

Section: Catalysismentioning

confidence: 97%

“…From then, an increasingly number of papers have appeared in the literature, demonstrating, inter-alia, by the publication of two reviews completely dedicated to the subject [ 7 , 18 ] with other reviews also dealing in part with the same theme [ 19 ]. Potential applications in organic synthesis, homogeneous catalysis, biomedicine, and advanced materials are revealing the hidden potentialities in this field.…”

Section: History Of Rollover Cyclometalationmentioning

confidence: 99%

“…At variance, Thiel and coworkers, in their review on the argument [ 18 ], proposed that the final step of the roll-over cyclometalation of aromatic nitrogen donors is analogous to a classical organic S E Ar reaction, where the metal acts as the electrophile. Therefore, “the more electron-rich the ring system is, the more reactive it should be.“ This is not in line with the extreme rapidity of the reaction of 6-CF 3 -2,2′-bipyridine with [PtMe 2 (DMSO) 2 ] (and even 5-CF 3 -2,2′-bipyridine) but it should be suitable on the basis that different metals (and also different metal precursors of the same metal) may act following different reaction mechanisms.…”

Section: Mechanism Of Rollover Cyclometalationmentioning

confidence: 99%

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Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Zucca

Pilo

2021

Molecules

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Rollover cyclometalation constitutes a particular case of cyclometallation reaction. This reaction occurs when a chelated heterocyclic ligand loses its bidentate coordination mode and undergoes an internal rotation, after which a remote C–H bond is regioselectively activated, affording an uncommon cyclometalated complex, called “rollover cyclometalated complex”. The key of the process is the internal rotation of the ligand, which occurs before the C–H bond activation and releases from coordination a donor atom. The new “rollover” ligand has peculiar properties, being a ligand with multiple personalities, no more a spectator in the reactivity of the complex. The main reason of this peculiarity is the presence of an uncoordinated donor atom (the one initially involved in the chelation), able to promote a series of reactions not available for classic cyclometalated complexes. The rollover reaction is highly regioselective, because the activated C–H bond is usually in a symmetric position with respect to the donor atom which detaches from the metal stating the rollover process. Due to this novel behavior, a series of potential applications have appeared in the literature, in fields such as catalysis, organic synthesis, and advanced materials.

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Section: Catalysismentioning

confidence: 97%

Section: History Of Rollover Cyclometalationmentioning

confidence: 99%

Section: Mechanism Of Rollover Cyclometalationmentioning

confidence: 99%

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Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Zucca

Pilo

2021

Molecules

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“…Interestingly, part of the synthesized compounds demonstrated moderate to high antibacterial and antifungal activities compared to standard drugs Gatifloxacin and Clotrimazole, respectively [76]. Palladacyclic complexes [77] have been described lately in a number of cross-coupling reactions. The Suzuki-Miyaura reaction of chloro uracil analogue with potassium aryltrifluoroborates (ArBF 3 K), was recently reported to be mediated in water.…”

Section: Suzuki Cross-coupling Reactionmentioning

confidence: 99%

“…Sodium tetraphenylborate was efficiently employed instead of ArB(OH) 2 , ArB(OR) 2 , or ArBF 3 K in the cross-coupling reaction with four-fold of aryl bromides in the presence of different palladium catalysts under microwave heating, yielding a variety of biaryl derivatives [80,81]. Palladacyclic complexes [77] have been described lately in a number of cross-coupling reactions. The Suzuki-Miyaura reaction of chloro uracil analogue with potassium aryltrifluoroborates (ArBF3K), was recently reported to be mediated in water.…”

Section: Suzuki Cross-coupling Reactionmentioning

confidence: 99%

Microwave-Assisted Palladium-Catalyzed Cross-Coupling Reactions: Generation of Carbon–Carbon Bond

Salih

Baqi

2019

Catalysts

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Cross-coupling reactions furnishing carbon–carbon (C–C) bond is one of the most challenging tasks in organic syntheses. The early developed reaction protocols by Negishi, Heck, Kumada, Sonogashira, Stille, Suzuki, and Hiyama, utilizing palladium or its salts as catalysis have, for decades, attracted and inspired researchers affiliated with academia and industry. Tremendous efforts have been paid to develop and achieve more sustainable reaction conditions, such as the reduction in energy consumption by applying the microwave irradiation technique. Chemical reactions under controlled microwave conditions dramatically reduce the reaction time and therefore resulting in increase in the yield of the desired product by minimizing the formation of side products. In this review, we mainly focus on the recent advances and applications of palladium catalyzed cross-coupling carbon–carbon bond formation under microwave technology.

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Transition‐Metal Catalyzed Reactions

González-Gómez

Alonso

2021

Organic Reaction Mechanisms Series

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Roll-over cyclometalation: A versatile tool to enhance the catalytic activity of transition metal complexes

Cited by 27 publications

References 94 publications

Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Microwave-Assisted Palladium-Catalyzed Cross-Coupling Reactions: Generation of Carbon–Carbon Bond

Transition‐Metal Catalyzed Reactions

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