Enantioselective Ketone Hydroacylation Using Noyori’s Transfer Hydrogenation Catalyst

Murphy, Stephen K.; Dong, Vy M.

doi:10.1021/ja4021974

Cited by 78 publications

(39 citation statements)

References 33 publications

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“…"Coumarin" is am ore commonly used name for the benzenoid lactones that are found in several essential oils. [64] Intramolecular cyclisation of phenoxyethynyl diols affords polysubstituted a,b-unsaturated g-lactones using AgOTf as ac atalyst (Scheme 6d). [61] Lactones are chemically stable because, as in all organic cyclic molecules, five-and six-membered rings minimise the strain arising from disfavoured bond angles.…”

Section: Pharmacological Profile Of Oxazolidinone Derivativesmentioning

confidence: 99%

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Singh

Silakari

2018

ChemMedChem

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O-Heterocycles have been explored in the field of medicinal chemistry for a long time, but their significance has not been duly recognised and they are often shunned in favour of N-heterocycles. The design of bioactive molecules for nearly every pathophysiological condition is primarily focused on novel N-heterocycles. The main reasons for such bias include the ease of synthesis and possible mimicking of physiological molecules by N-heterocycles. But considering only this criterion rarely provides breakthrough molecules for a given disease condition, and instead the risks of toxicity or side effects are increased with such molecules. On the other hand, owing to improved synthetic feasibility, O-heterocycles have established themselves as equally potent lead molecules for a wide range of pathophysiological conditions. In the last decade there have been hundreds of reports validating the fact that equally potent molecules can be designed and developed by using O-heterocycles, and these are also expected to have comparably low toxicity. Even so, researchers tend to remain biased toward the use of N-heterocycles over O-heterocycles. Thus, this review provides a critical analysis of the synthesis and medicinal attributes of O-heterocycles, such as pyrones, oxazolones, furanones, oxetanes, oxazolidinones, and dioxolonones, and others, reported in the last five years, underlining the need for and the advantages guiding researchers toward them.

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Section: Pharmacological Profile Of Oxazolidinone Derivativesmentioning

confidence: 99%

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Singh

Silakari

2018

ChemMedChem

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“…1,4-keto alcohols are precursors for 1,4-keto aldehydes,w hich are sensitive to decomposition through an aldol-type pathway.T he mechanism consists of Noyoris transfer hydrogenation of the ketone followed by oxidation of the primary alcohol, thus leading to formation of alactone via the hemiacetal intermediate 83. [39] Scheme 9. Synthesis of N-heterocycles by isomerization/Michael addition of amide-tethered propargyl alcohols.…”

Section: Annulation By Oxidative Cyclization Of Alcoholsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Hydrogen‐Transfer Annulations: Access to Heterocyclic Scaffolds

et al. 2015

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The ability of hydrogen-transfer transition-metal catalysts, which enable increasingly rapid access to important structural scaffolds from simple starting materials, has led to a plethora of research efforts on the construction of heterocyclic scaffolds. Transition-metal-catalyzed hydrogen-transfer annulations are environmentally benign and highly atom-economical as they release of water and hydrogen as by-product and utilize renewable feedstock alcohols as starting materials. Recent advances in this field with respect to the annulations of alcohols with various nucleophilic partners, thus leading to the formation of heterocyclic scaffolds, are highlighted herein.

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“…Experimentally, many transition metals have been reported to catalyze the intra-or inter-molecular hydroacylation, e.g. cobalt, 13,14 nickel, [15][16][17] copper, 18,19 ruthenium, [20][21][22][23][24][25] rhodium, [26][27][28][29][30][31] palladium, 32,33 iridium 34 and gold. 35 In 2007, Ryu et al reported the regioselective addition of aldehydes to enones catalyzed by the ruthenium hydride complex RuHCl(CO)(PPh 3 Þ 3 leading to 1, 3diketones.…”

Section: Introductionmentioning

confidence: 99%

“…21 Soon after that, Ryu et al also reported ruthenium hydride-catalyzed hydroacylation of aldehydes to dienes forming ,-unsaturated ketones 22 and Krische et al attempted ruthenium-catalyzed diene hydroacylation from an alcohol or aldehyde. 23 Recently, Dong et al investigated the enantioselective ketone hydroacylation using Noyori's transfer hydrogenation catalyst and the regioselective alkyne hydroacylation by Tandem ruthenium catalysis. 24,25 Hyatt et al investigated theoretically rhodium(I)-catalyzed hydroacylation of alkenes, and proved that the reductive elimination was the rate-determining step.…”

Section: Introductionmentioning

confidence: 99%

Substituent effect and ligand exchange control the reactivity in ruthenium(II)-catalyzed hydroacylation of isoprenes and aldehydes ‖ A DFT study

Meng

Wang

et al. 2016

J. Theor. Comput. Chem.

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Density functional theory (DFT) was used to investigate the reaction mechanisms of ruthenium (II)-catalyzed hydroacylation of isoprene with benzaldehyde, and o-methoxyl, m-methoxyl and p-methoxyl benzaldehyde. All intermediates and transition states were entirely optimized at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Ru). The results demonstrated that the hydroacylation had two di®erent catalytic cycles (path I and II), path II was more favorable than path I. Ru(II)-catalyzed hydroacylation began from the¯rst catalytic cycle, and the nucleophilic reaction was the rate-determining step. The activation barriers of hydrogen migration were the highest in two catalytic cycles, so the hydrogen migration was the rate-determining step. The activation barrier of hydrogen migration could be broken down to two parts: the free energy of exchange (ÁG ex ) and the relative free energy of transition state (ÁG). The ligand exchange energy (ÁG ex ) had more contribution to the activation barrier than the relative free energy of transition state (ÁG), so the ligand exchange would control these hydroacylation. Furthermore, our calculations also described the substituent e®ect, and the results indicated that four aldehydes showed di®erent chemical reactivity, and benzaldehyde and m-methoxyl benzaldehyde were predicted to have the best reactivity in ruthenium hydride-catalyzed hydroacylation.

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Enantioselective Ketone Hydroacylation Using Noyori’s Transfer Hydrogenation Catalyst

Cited by 78 publications

References 33 publications

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

The Current Status of O‐Heterocycles: A Synthetic and Medicinal Overview

Transition‐Metal‐Catalyzed Hydrogen‐Transfer Annulations: Access to Heterocyclic Scaffolds

Substituent effect and ligand exchange control the reactivity in ruthenium(II)-catalyzed hydroacylation of isoprenes and aldehydes ‖ A DFT study

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