Regioselective Hydroacylation of 1,3-Dienes by Cobalt Catalysis

Chen, Qing‐An; Kim, Daniel K.; Dong, Vy M.

doi:10.1021/ja500268w

Cited by 161 publications

(83 citation statements)

References 99 publications

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“…Switching to ferrocene-based ligands gave the desired β,γ-unsaturated product 3aa (entries 3–6). 22 Josiphos L1 provided the highest reactivity and regioselectivity (entry 5). Removing the backbone methyl group in Josiphos L1 resulted in a decrease in regioselectivity (entry 7 vs 5).…”

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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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Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

2015

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“…[1] Our laboratory has previously focused on the oxidation of aldehydes under Rh, Ru, and Co-catalysis. [2] Inspired by the promise of base metals, we considered that Ni-catalyzed cross-coupling of aldehydes could be classified into three general types: redox neutral, reductive, and oxidative (Figure 1). For example, Ogoshi's cross-coupling between two aldehydes is a redox neutral method that generates ester bonds.…”

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Nickel‐Catalyzed Dehydrogenative Cross‐Coupling: Direct Transformation of Aldehydes into Esters and Amides

2014

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By exploring a new mode of Ni-catalyzed cross-coupling, we have developed a protocol to transform both aromatic and aliphatic aldehydes into either esters or amides directly. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. We present mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C–H bond.

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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.…”

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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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Regioselective Hydroacylation of 1,3-Dienes by Cobalt Catalysis

Cited by 161 publications

References 99 publications

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

Nickel‐Catalyzed Dehydrogenative Cross‐Coupling: Direct Transformation of Aldehydes into Esters and Amides

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

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