Synthesis of methyl β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH2CH2C(R)=CH2

Nifant’ev, Ilya E.; Sevostyanova, N. T.; Баташев, С. А.; Vinogradov, A.; Churakov, Andrei V.; Ivchenko, Pavel V.

doi:10.1016/j.apcata.2019.05.030

Cited by 17 publications

(7 citation statements)

References 80 publications

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“…The best results, a 92% yield with 99% selectivity, were obtained using a (acac)Rh(CO) 2 /PPh 3 catalyst [175]. The closely related methoxycarbonylation of methylenealkanes (Scheme 12b) was accompanied by the isomerization of the starting hydrocarbons; the rational design of the Pd/diphosphine catalyst had made it possible to reach average yields of the branched methyl esters [176]. The esters obtained were used in the synthesis of Group 5 oil base stocks with promising viscosity characteristics [177].…”

Section: Catalytic Transformations Of Methylenealkanesmentioning

confidence: 99%

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Fair Look at Coordination Oligomerization of Higher α-Olefins

Nifant’ev

Ivchenko

2020

Polymers

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Coordination catalysis is a highly efficient alternative to more traditional acid catalysis in the oligomerization of α-olefins. The distinct advantage of transition metal-based catalysts is the structural homogeneity of the oligomers. Given the great diversity of the catalysts and option of varying the reaction conditions, a wide spectrum of processes can be implemented. In recent years, both methylenealkanes (vinylidene dimers of α-olefins) and structurally uniform oligomers with the desired degrees of polymerization have become available for later use in the synthesis of amphiphilic organic compounds and polymers, high-quality oils or lubricants, and other prospective materials. In the present review, we discussed the selective dimerization and oligomerization of α-olefins, catalyzed by metallocene and post-metallocene complexes, and explored the prospects for the further applications of the coordination α-olefin dimers and oligomers.

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Section: Catalytic Transformations Of Methylenealkanesmentioning

confidence: 99%

“…Catalytic transformations of methylenealkanes: (a) Hydrofirmylation[173,175]; (b) Methoxycarbonylation[176]; (c) Hydrosilylation[178].…”

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confidence: 99%

Fair Look at Coordination Oligomerization of Higher α-Olefins

Nifant’ev

Ivchenko

2020

Polymers

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“…[13,15] Similarly, the catalytic process has employed mostly in situ generated active catalysts from the reactions of various of palladium(II) metal salts and the phosphine-based ligands. [16][17][18][19][20] However, despite the success of these phosphine-based palladium(II) catalysts, they are not without any blemish. Key among the limitations is the relatively high costs of their establishment, in addition to their isolation and handling.…”

Section: Introductionmentioning

confidence: 99%

Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins

Akiri

Ojwach

2021

Applied Organom Chemis

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Reactions of ligands (E)‐N′‐(2,6‐diisopropylphenyl)‐N‐(4‐methylpyridin‐2‐yl)benzimidamide (L1), (E)‐N′‐(2,6‐diisopropylphenyl)‐N‐(6‐methylpyridin‐2‐yl)benzimidamide (L2), (E)‐N′‐(2,6‐dimethylphenyl)‐N‐(6‐methylpyridin‐2‐yl)benzimidamide (L3), (E)‐N′‐(2,6‐dimethylphenyl)‐N‐(4‐methylpyridin‐2‐yl)benzimidamide (L4), and (E)‐N‐(6‐methylpyridin‐2‐yl)‐N′‐phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para‐tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.

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“…Recently [46], we reported an efficient method of catalytic methoxycarbonylation of methylenealkanes with regioselective formation of the corresponding methyl esters (Scheme 2c). In contrast with the hydroformylation/reduction sequence reported earlier [43][44][45] (Scheme 2b), our approach (Scheme 2c) allows obtaining the esters that contain methylenealkane-derived branched alkyl in acid or in alcohol fragment ot the molecule.…”

Section: Introductionmentioning

confidence: 99%

Methylenealkane-Based Low-Viscosity Ester Oils: Synthesis and Outlook

et al. 2020

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Both Group 4 poly-α-olefin (PAO) and Group 5 ester oil basestocks are used in formulations of synthetic engine oils, transmission fluids, and lubricants with leading characteristics such as low viscosity (providing fuel saving), high stability, and environmental safety. The modern technologies of the production of PAOs use catalytic oligomerization of α-olefins, which is complicated by the formation of low-molecular-weight α-olefin dimers (methylenealkanes) as imminent side products. The use of methylenealkanes as raw materials for the synthesis of Group 5 base stocks appears to be highly promising. In the present work, we report the use of methyl 3-butylnonanoate and methyl 3-hexylundecanoate, the products of catalytic methoxycarbonylation of hex-1-ene and oct-1-ene dimers, in the synthesis of two series of branched isomeric esters. These esters demonstrated excellent rheological behavior and may be considered as low-viscosity engine oils with leading characteristics.

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Synthesis of methyl β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH2CH2C(R)=CH2

Cited by 17 publications

References 80 publications

Fair Look at Coordination Oligomerization of Higher α-Olefins

Fair Look at Coordination Oligomerization of Higher α-Olefins

Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins

Methylenealkane-Based Low-Viscosity Ester Oils: Synthesis and Outlook

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