Synthesis and Application of Stereoretentive Ruthenium Catalysts on the Basis of the M7 and the Ru–Benzylidene–Oxazinone Design

Dumas, Adrien; Müller, Daniel S.; Curbet, Idriss; Toupet, Loı̈c; Rouen, Mathieu; Baslé, Olivier; Mauduit, Marc

doi:10.1021/acs.organomet.7b00836

Cited by 8 publications

(8 citation statements)

References 57 publications

(18 reference statements)

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“…We were surprised by the very low activity of all new uNHC- and CAAC-based catalysts, whichwith the exception of Ru10 gave conversions below 40%. Despite the resulting E / Z stereoselectivity being very high in all cases ( E / Z = 5/95, which corresponds to the E / Z ratio of 4/96 reported for Ru4a in the literature), such low chemical activity seems to be disqualifying for practical applications.…”

Section: Resultsmentioning

confidence: 99%

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Unexpected Latency of Z-Stereoretentive Ruthenium Olefin Metathesis Catalysts Bearing Unsymmetrical N-heterocyclic Carbene or Cyclic(alkyl)(amino)carbene Ligands

et al. 2022

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A set of ruthenium complexes bearing a CAAC or uNHC ligand and a dithiocatechol fragment have been obtained and characterized spectroscopically. The activity and Z-selectivity of the newly obtained catalysts were studied in selected model CM, self-CM, and RCM olefin metathesis reactions. Intriguingly, and in contrast to structurally related NHC-bearing catalysts Ru4a and Ru4b, the CAAC and uNHC analogues showed no or only very little activity in olefin metathesis. Interestingly, despite being not productive in metathesis reactions conducted in solution, Ru8 enabled the synthesis of a model 16-membered macrocyclic lactone of valuable musk smell with excellent chemoselectivity (no C–C double-bond migration was observed) at a concentration 40 times higher than that typically used by organic chemists in similar macrocyclizations (200 mM instead of 5 mM) with excellent Z-selectivity. Unfortunately, also here the conversion was low.

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Section: Resultsmentioning

confidence: 99%

“… a Conversion reported in the literature b Conversions were determined by GC with tetradecane used as an internal standard. …”

Section: Resultsmentioning

confidence: 99%

Unexpected Latency of Z-Stereoretentive Ruthenium Olefin Metathesis Catalysts Bearing Unsymmetrical N-heterocyclic Carbene or Cyclic(alkyl)(amino)carbene Ligands

et al. 2022

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“…Variation of sterically demanding catecholthiolate ligands was reported by Grubbs in 2017 (e.g., Ru-11 ) [11]. In 2018 our group reported a series of electronically and sterically activated dithiolate ruthenium catalysts (e.g., Ru-12 ) [12]. However, none of these studies identified more efficient or practical catalysts compared to the ones shown in Fig.…”

Section: Reviewmentioning

confidence: 92%

A tutorial review of stereoretentive olefin metathesis based on ruthenium dithiolate catalysts

Müller¹,

Baslé²,

Mauduit³

2018

Beilstein J. Org. Chem.

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Stereoretentive olefin metathesis based on ruthenium dithiolate complexes has become a very active field of research within the past years. This unique catalyst class is able to kinetically produce both Z- and E-alkenes in high stereochemical purity (typically >95:5) starting from stereochemically pure Z- or E-alkenes. The aim of this tutorial review is to organize the reported information concerning ruthenium dithiolate catalysts in a logic manner, thus providing an "operators handbook" for chemists who wish to apply this methodology in synthesis.

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“…To probe the impact of air on metathesis by the H 2 IPr and H 2 IMes derivatives Ru-2a / b , we first evaluated the impact of the atmosphere on representative reactions involving terminal or internal olefins under standard conditions . For the cross-metathesis of cis -1,4-butenediol with allylbenzene (Scheme a), yields after 4 h for reactions in THF in air were approximately half those obtained under inert atmosphere.…”

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confidence: 99%

Rapid Aerial Oxidation of Ruthenium-Dithiocatecholate Catalysts: A Challenge to Stereoretentive Olefin Metathesis

2023

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Ruthenium dithiolene complexes, particularly the dithiocatecholates Ru(S 2 C 6 H 2 -3,6-Cl 2 )(NHC)(=CHC 6 H 4 -2-O i Pr) (NHC = H 2 IPr, H 2 IMes), are an important class of olefin metathesis catalysts employed for the stereocontrolled assembly of C=C bonds. The poorly understood sensitivity of these catalysts results in unpredictable performance. Here they are shown to resist degradation by amine nucleophiles, in contrast with their dichloride parents; however, they are significantly more oxygen-sensitive. Even as the precatalysts, they decompose within minutes in solution under O 2 , eliminating the alkylidene ligand as O=CHC 6 H 4 -2-O i Pr and forming unusual, fourcoordinate Ru(IV)-oxo products, Ru(O)(S 2 C 6 H 2 -3,6-Cl 2 )(NHC). Participation of the latter in O-transfer with PPh 3 suggests potential opportunities in catalytic oxidation.

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Synthesis and Application of Stereoretentive Ruthenium Catalysts on the Basis of the M7 and the Ru–Benzylidene–Oxazinone Design

Cited by 8 publications

References 57 publications

Unexpected Latency of Z-Stereoretentive Ruthenium Olefin Metathesis Catalysts Bearing Unsymmetrical N-heterocyclic Carbene or Cyclic(alkyl)(amino)carbene Ligands

Unexpected Latency of Z-Stereoretentive Ruthenium Olefin Metathesis Catalysts Bearing Unsymmetrical N-heterocyclic Carbene or Cyclic(alkyl)(amino)carbene Ligands

A tutorial review of stereoretentive olefin metathesis based on ruthenium dithiolate catalysts

Rapid Aerial Oxidation of Ruthenium-Dithiocatecholate Catalysts: A Challenge to Stereoretentive Olefin Metathesis

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