Enantioselective hydroacylation of olefins with rhodium catalysts

Murphy, Stephen K.; Dong, Vy M.

doi:10.1039/c4cc02276a

Cited by 115 publications

(44 citation statements)

References 51 publications

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“…The hydroacylation of alkenes with aldehydes is an atom‐economical approach for the synthesis of valuable ketones . Although many examples of intra molecular hydroacylation have been reported, the inter molecular variant of this reaction is often plagued by undesired aldehyde decarbonylation pathways …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

Delius

Ellinger

et al. 2017

Israel Journal of Chemistry

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Cytosporone B and its simple analogues (e. g., amoitone B) were recently identified as unique agonists for nuclear orphan receptor Nur77. In this study, we have developed an aldehyde C‐H activation method for preparing natural and designer analogues from the cytosporone family. In addition, a comprehensive investigation of the compounds’ biological activities and pharmacological liabilities has been conducted and new structure activity relationships (SAR) were derived from the data. Most notably, we found that increased cytotoxicity can be obtained by virtue of fluorine substitution on the hydrophobic acyl chain.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

Delius

Ellinger

et al. 2017

Israel Journal of Chemistry

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“…14 Since the first example of this transformation reported by Sakai in 1972, the reaction has been extensively studied by using rhodium catalysts. 15 However, owing to the fact that acyl-rhodium intermediates tend to undergo undesired decarbonylation during the course of intermolecular reactions, aldehydes used in the reactions usually need additional coordinating groups. To address this limitation of substrates, we envisioned developing efficient intermolecular hydroacylations of alkenes with simple aldehydes that do not have coordinating groups.…”

Section: Nickel(0)-catalyzed Hydroacylation Of Styrenes With Simple Amentioning

confidence: 99%

Nickel-Catalyzed Highly Atom-Economical C–C Coupling Reactions with π Components

Xiao

Zhou

2018

Synlett

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b 0 0 0 0 -0 0 0 2 -4 7 0 0 -3 7 6 5Abstract This account describes our latest advances in the field of nickel(0)-catalyzed hydrofunctionalization of π components. All reactions proceed either through internal hydride transfer or by using an external proton as the hydride source, thereby eliminating the use of stoichiometric amounts of reductants or oxidants. These nickel-catalyzed atom-economical coupling reactions demonstrate that nickel not only is an inexpensive metal catalyst, but also possesses unique and versatile catalytic abilities. Current limitations and the outlook of these reactions are also discussed.

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“…[1][2][3][4][5][6][7][8][9][10][11] Hydroacylation is one of the most useful C-H bond activation processes, [7][8][9][10][11] and represents an ordinary, green, atom-e±cient synthetic approach. 12 Enormous e®orts have been devoted to develop more convenient and e±cient strategies for catalytic hydroacylation.…”

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 hydroacylation of olefins with rhodium catalysts

Abstract: Rh-catalysed hydroacylation allows the construction of chiral ketones from olefins and aldehydes. Since James' and Young's serendipitous discovery of the enantioselective 4-pentenal cyclisation, both intra and intermolecular variants have emerged that enable broader applications.

Cited by 115 publications

References 51 publications

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

Nickel-Catalyzed Highly Atom-Economical C–C Coupling Reactions with π Components

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

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