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We describe the total synthesis of (+)- and (-)-galbulimima alkaloid 13. The absolute stereochemistry of natural (-)-galbulimima alkaloid 13 is revised to 2S. Sequential use of catalytic cross-coupling and cross-metathesis reactions followed by an intramolecular Diels-Alder reaction provided the required trans-decalin AB-ring system and masked the C16 carbonyl as an N-vinyl carbamate for late-stage unveiling in the form of the necessary C16 enone. A vinyl radical cyclization secured the C-ring, while successful execution of our strategy for introduction of the CDE-ring system in complex galbulimima alkaloids provided the target pentacycle with complete diastereoselection. Copyright

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Archives for Chemistry Experiments of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The correlation between rapid initiation and rapid decomposition in olefin metathesis is probed for a series of fast-initiating, phosphine-free Ru catalysts: the Hoveyda catalyst HII, RuCl2(L)(=CHC6H4-o-OiPr); the Grela catalyst nG (a derivative of HII with a nitro group para to OiPr); the Piers catalyst PII, [RuCl2(L)(=CHPCy3)]OTf; the third-generation Grubbs catalyst GIII, RuCl2(L)(py)2(=CHPh); and dianiline catalyst DA, RuCl2(L)(o-dianiline)(=CHPh), in all of which L = H2IMes = N,N?-bis(mesityl)imidazolin-2-ylidene. Prior studies of ethylene metathesis have established that various Ru metathesis catalysts can decompose by beta-elimination of propene from the metallacyclobutane intermediate RuCl2(H2IMes)(kappa2-C3H6), Ru-2. The present work demonstrates that in metathesis of terminal olefins, beta-elimination yields only ca. 25-40% propenes for HII, nG, PII, or DA, and none for GIII. The discrepancy is attributed to competing decomposition via bimolecular coupling of methylidene intermediate RuCl2(H2IMes)(=CH2), Ru-1. Direct evidence for methylidene coupling is presented, via the controlled decomposition of transiently stabilized adducts of Ru-1, RuCl2(H2IMes)Ln(=CH2) (Ln = pyn?; n? = 1, 2, or o-dianiline). These adducts were synthesized by treating in situ-generated metallacyclobutane Ru-2 with pyridine or o-dianiline, and were isolated by precipitating at low temperature (-116 or -78 C, respectively). On warming, both undergo methylidene coupling, liberating ethylene and forming RuCl2(H2IMes)Ln. A mechanism is proposed based on kinetic studies and molecular-level computational analysis. Bimolecular coupling emerges as an important contributor to the instability of Ru-1, and a potentially major pathway for decomposition of fast-initiating, phosphine-free metathesis catalysts.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Patent,once mentioned of 301224-40-8, Quality Control of: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

Provided herein is a method of producing C11, C12, and C13 nylon precursors from oleic acid or esters of oleic acid, the method involving amide formation, ring-closing metathesis, and hydrogenation. Further provided are the products of the method described. Provided herein is a method for producing a lactam, the method comprising the steps of converting oleic acid or an ester of oleic acid into an amide having a general formula of H3C-(CH2)rCH=CH-(CH2)rCONR-(CH2)n-CH=CH2, wherein n is 1, 2, or 3, and R is either hydrogen or benzyl; subjecting the amide to a ring-closing metathesis reaction to produce an intermediate having a general formula of -(CH2)rCONR-(CH2) n-CH=CH2-, wherein n is 1, 2, or 3, R is either hydrogen or benzyl, and both ends are connected to each other; and hydrogenating the intermediate to produce a saturated lactam. In certain embodiments, the saturated lactam has a formula of -NH-(CH2) 10-CO-.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A series of ruthenium olefin metathesis catalysts bearing N-heterocycliccarbene (NHC) ligands with varying degrees of backbone and N-aryl subst itution have been prepared. These complexes show greater resistance to decomposition through C-H activation of the N-aryl group, resulting in increased catalyst lifetimes. This work has utilized robotic technology toexamine the activity and stability of each catalyst in metathesis, prov iding insights into the relationship between ligand architecture and enhanced efficiency. The development of this robotic methodology has also shown that, under optimized conditions, catalyst loadings as low as 25 ppm can lead to 100percent conversion in the ring-closing metathesis of diethyl diallylmalonate.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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(Chemical Presented) The unique 16-membered macrolide (+)-exiguolide (1) was the target of a total synthesis featuring radical and Prins cyclizations of beta-alkoxyacrylates, along with ring-closing olefin metathesis. The structure incorporates two cis-2,6-disubstituted oxane rings where one of the rings has an exocyclic enoate group. The successful synthesis of 1, isolated from a marine sponge, led to the unambiguous determination of its absolute stereochemistry.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Grubbs-Hoveyda-type complexes with variable 4-R (complexes 1: 4-R = NEt2, OiPr, H, F, NO2) and 5-R substituents (complexes 2: 5-R = NEt2, OiPr, Me, F, NO2) at the 2-isopropoxy benzylidene ether ligand and with variable 4-R substituents (complexes 3: 4-R = H, NO2) at the 2-methoxy benzylidene ether ligand were synthesized and the respective Ru(II/III) redox potentials (ranging from DeltaE = +0.46 to +1.04 V), and UV-vis spectra recorded. The initiation kinetics of complexes 1-3 with the olefins diethyl diallyl malonate (DEDAM), butyl vinyl ether (BuVE), 1-hexene, styrene, and 3,3-dimethylbut-1-ene were investigated using UV-vis spectroscopy. Electron-withdrawing groups at the benzylidene ether ligands were found to increase the initiation rates, while electron-donating groups lead to slower precatalyst activation; accordingly with DEDAM, the complex 1(NO 2) initiates almost 100 times faster than 1(NEt2). The 4-R substituents (para to the benzylidene carbon) were found to have a stronger influence on physical and kinetic properties of complexes 1 and 2 than that of 5-R groups para to the ether oxygen. The DEDAM-induced initiation reactions of complexes 1 and 2 are classified as two-step reactions with an element of reversibility. The hyperbolic fit of the kobs vs [DEDAM] plots is interpreted according to a dissociative mechanism (D). Kinetic studies employing BuVE showed that the initiation reactions simultaneously follow two different mechanistic pathways, since the kobs vs [olefin] plots are best fitted to kobs = kD·k4/k -D·[olefin]/(1 + k4/k-D·[olefin]) + kI·[olefin]. The kI·[olefin] term dominates the initiation behavior of the sterically less demanding complexes 3 and was shown to correspond to an interchange mechanism with associative mode of activation (Ia), leading to very fast precatalyst activation at high olefin concentrations. Equilibrium and rate constants for the reactions of complexes 1-3 with the bulky PCy3 were determined. In general, sterically demanding olefins (DEDAM, styrene) and Grubbs-Hoveyda type complexes 1 and 2 preferentially initiate according to the dissociative pathway; for the less bulky olefins (BuVE, 1-hexene) and complexes 1 and 2 both D and I a are important. Activation parameters for BuVE reactions and complexes 1(NEt2), 1(H), and 1(NO2) were determined, and DeltaS? was found to be negative (DeltaS ? = -113 to -167 J·K-1·mol -1) providing additional support for the Ia catalyst activation.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The first enantioselective total synthesis of lycopodine has been completed. Key steps include a highly diastereoselective organocatalyzed cyclization of a keto sulfone to establish the key C7 and C8 stereocenters and a tandem 1,3-sulfonyl shift/intramolecular Mannich cyclization to form the tricyclic core. Copyright

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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In this study we report the catalytic performance, reaction engineering kinetics and elucidation of the reaction mechanism using density functional theory (DFT) for the metathesis reaction of 1-octene in the presence of the Hoveyda-Grubbs 2 [RuCl2(CHoOiPrC6H 4)(H2IMes)] precatalyst. The study showed that reaction temperature (30-100 C), 1-octene/precatalyst molar ratio (5000-14,000) and different solvents had a significant effect on the selectivity, activity and turnover number. Turnover numbers as high as 6448 were observed. Two main reactions were observed, namely: metathesis over the entire temperature range and isomerization above 50 C. The observed experimental product-time distribution data for the complex parallel reaction system was fairly accurately described by four pseudo-first order reaction rates. The effects of temperature (Arrhenius Equation) and precatalyst concentration were incorporated in the observed rate constant. The primary observed activation energy was approximately 24 kcal mol-1, which is in agreement with the DFT computational values for the proposed Hoveyda-Grubbs mechanism.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Patent,once mentioned of 301224-40-8, Quality Control of: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

The present invention provides a process for preparing cycloheptene and derivatives thereof by ring-closing metathesis of unsymmetric 1,8-dienes whose C?C double bond at the 8 position is nonterminal. Cycloheptene and the cycloheptanone, cycloheptylamine, cycloheptanecarbaldehyde, cycloheptanecarboxylic acid and cycloheptanecarbonyl chloride conversion products thereof, and the derivatives thereof, are important synthesis units for active ingredient compounds. The ring-closing metathesis is preferably performed as a reactive distillation. The unsymmetric 1,8-dienes for the ring-closing metathesis can be obtained by catalytic decarbonylation or oxidative decarboxylation from the corresponding unsaturated carboxylic acids or carboxylic acid derivatives.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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An olefin metathesis catalyst bearing a tridentate hemilabile N-heterocyclic carbene (NHC) ligand was synthesized and characterized. The solid-state crystal structure reveals coordination from all three donation sites of the NHC ligand, giving rise to a stable 18-electron complex. Catalytic activity in three standard metathesis reactions was demonstrated, revealing our catalyst to be particularly long lived and highly selective in the self-metathesis of 1-decene. Although the catalyst in this work initiates more slowly than its second-generation counterparts, it was shown to have high thermal stability, yielding peak performances at higher temperatures. The unique ligand framework of this catalyst may serve as a template for the synthesis of analogous catalysts with improved efficiencies.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI