Catalytic intermolecular hydroacylation of C–C π-bonds in the absence of chelation assistance

Leung, Joyce C.; Krische, Michael J.

doi:10.1039/c2sc20350b

Cited by 234 publications

(89 citation statements)

References 135 publications

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“…4 It occurred to us that tandem catalysis 5 could be used to overcome challenges in hydroacylation, the addition of an aldehyde C–H bond across an unsaturated π-bond. 6 Towards expanding ketone hydroacylation, we reported a cascade involving alcohol oxidation, enantioselective ketone reduction, and lactol oxidation to generate lactones, a process in which all three transformations were promoted by Noyori’s Ru-catalyst. 5a Herein, we apply tandem Ru-catalysis to achieve the hydroacylation of alkynes with unprecedented regiocontrol to afford β,γ-unsaturated ketones.…”

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confidence: 99%

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

2015

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By using tandem ruthenium-catalysis, internal alkynes can be coupled with aldehydes for the synthesis of β,γ-unsaturated ketones. The catalyst promotes alkyne transformations with high regioselectivity, with examples that include the differentiation of a methyl versus ethyl substituent on the alkyne. Mechanistic studies suggest that the regioselectivity results from a selective allene formation that is governed by allylic strain.

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confidence: 99%

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

2015

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“…Oxidative coupling-metalacycle fragmentation pathways are proposed for the hydrogen-mediated processes, whereas the copper catalyzed reactions are postulated to operate via olefin hydrometalation to form σ-benzyl copper intermediates. While hydroacylations employing aldehydes as acyl donors require chelating groups to suppress conversion of the transient acyl metal intermediates to catalytically inactive carbonyl complexes, the present anhydride reductive couplings overcome this limitation (17). …”

Section: α-Olefins and Styrenesmentioning

confidence: 99%

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Nguyen

Park

Luong

et al. 2016

Science

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315

120

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α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

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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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Catalytic intermolecular hydroacylation of C–C π-bonds in the absence of chelation assistance

Cited by 234 publications

References 135 publications

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

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

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