Metals in organic syntheses I. Propene hydrocarboxylation with various alkanols and PdCl2(PPh3)2 as catalyst precursor

doi:10.1016/0304-5102(79)80018-8

Journal of Molecular Catalysis

Volume 6, Issue 2, August 1979, Pages 111-122

https://doi.org/10.1016/0304-5102(79)80018-8 Get rights and content

Abstract

The hydrocarboxylation of propene with PdCl₂(PPh₃)₂ as catalyst precursor has been studied with MeOH, EtOH, n- and iso-PrOH, and n-, iso-, s-, and t-BuOH. this reaction occurs in high yields in every case, except with t-BuOH, in 3 – 15 h, at 90 – 130 °C, under P_CO ranging from ca 120 at ca. 40 atm. Qualitative observations indicate the following apparent reactivity order: primary > secondary > tertiary alcohols.

The selectivity towards the straight-chain isomer increases on (i), decreasing the temperature or (ii) increasing the catalyst concentration; when n-BuOh is used the selectivity is insensitive to P_CO in the range studied (40 – 120), insensitive to HCl when added in 2 equivalents per mole of catalyst precursor, and increases in the presence of PPh₃.

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Synthesis of methyl Β-alkylcarboxylates by Pd/diphosphine-catalyzed methoxycarbonylation of methylenealkanes RCH<inf>2</inf>CH<inf>2</inf>C(R)=CH<inf>2</inf>
2019, Applied Catalysis A: General
Citation Excerpt :
We propose that Cl–, in contrast to OAc–, can not hinder the coordination of the bulky methylenealkane molecule. However, the formation of HCl in the case of PdCl2/L/H2 catalysts (Scheme 6A) [26,35,86] results in protonation of 1 with subsequent isomerization by cationic mechanism. In summary, in the case of methylenealkanes in the presence of the PdCl2/L/H2 catalyst system, two reactions occur simultaneously: the target methoxycarbonylation and the acid-catalyzed isomerization.
A series of methylenealkanes RCH₂CH₂(R)C = CH₂ (R = n-butyl, n-hexyl, isopropyl and isobutyl), which are products of selective zirconocene-catalyzed dimerization of α-olefins, were introduced into Pd-catalyzed methoxycarbonylation. With the use of 5-methyleneundecane (1-hexene dimer) as a substrate, the roles of protic acid, Lewis acid and molecular hydrogen were established for model Pd(II)/PPh₃ and Pd(II)/diphosphine catalysts.
A series of bridged diphosphines were studied as catalyst components L in PdCl₂/L-catalyzed methoxycarbonylation in the presence of H₂. One of the nine diphosphines studied, trans-2,3-bis(diphenylphosphinomethyl)norbornane, demonstrated the best catalytic results in terms of catalytic activity, selectivity and isolated yields of the products. Under the optimized conditions during 24 h experiments, dimers RCH₂CH₂(R)C = CH₂ were transformed to methyl carboxylates RCH₂CH₂(R)CHCH₂COOMe with 99+% regioselectivity; isolated yields were 62–81%.
In that way, the catalytic methoxycarbonylation of synthetically available methylenealkanes is an effective approach to branched carboxylic acids, with high prospects for practical application.
Diastereoselective hydroalkoxycarbonylation of terpenes and vinyl-estrone
2001, Journal of Molecular Catalysis A: Chemical
Hydroalkoxycarbonylation of several monoterpenes (limonene, carvone, dihydrocarvone, pulegone) has been carried out with chiral and achiral palladium–phosphine catalysts. Despite high chemo- and regioselectivities toward the chiral linear products, diastereoselectivity is rather low and cannot be influenced significantly by the selection of the chiral ligand. This observation is in contrast with the high diastereoselectivity of the hydroalkoxycarbonylation of vinyl-estrone used as a model of a vinyl-aromatic skeleton.
Carbon monoxide as a building block in organic synthesis. Part II. One-step synthesis of esters by alkoxycarbonylation of naturally occurring allylbenzenes, propenylbenzenes and monoterpenes
1993, Journal of Molecular Catalysis
Various allylbenzenes (estragole, eugenol, eugenol methyl ether, safrole), propenylbenzenes (the iso compounds) and monoterpenes (limonene, isopulegol, isopulegyl acetate) were converted into the corresponding esters by alkoxycarbonylation at 4 MPa and 100 °C. Two palladium systems were used to catalyze this reaction: [PdCl₂(PPh₃)₂] and [PdCl₂(PPh₃)₂]/SnCl₂·2H₂O when larger amounts of linear ester are expected. This reaction was shown to be highly selective, since only the terminal carbon—carbon double bond was transformed. Isopulegol gave rise to a cyclocarbonylation reaction leading to the corresponding δ-lactone.
On the mechanism of the hydrocarbalkoxylation of olefins catalyzed by palladium complexes
1990, Journal of Organometallic Chemistry
The acyl complex PdCl(COR)(PPh₃)₂ (R = Et, n-Hex), isolated during the course of hydrocarbalkoxylation reactions catalyzed by the precursor system PdCl₂(PPh₃)₂-PPh₃ (95°C, P(CO) 100–120 atm; Pd: P = 1:3–4), in ethanol or higher alkanols as solvents, reacts with an alkanol R'OH in the presence of added PPh₃ (Pd: P = 1:3) to yield the ester RCOOR′and a mixture of PdCl₂(PPh₂)₂ and Pd(PPh₃)_{3 or 4}. Moreover, when it is employed as catalyst precursor (R = n-Hex; Pd: P = 1:4) in the hydrocarbalkoxylation of ethylene, it is recovered as its ethyl analog and it yields almost stoichiometric amounts of n-HexCOOR′. When the di carbomethoxy complex PdCl(COOMe)(PPh₃)₂, isolated in mixture with PdCl(COR)(PPh₃)₂ in hydrocarbomethoxylation experiments, is treated with 1-hexene in methanol (Pd: P:1-hexene : MeOH = 1:3:40:125), under nitrogen, in the absence of carbon monoxide, at 95°C, methyl heptanoate ester is not formed, and the starting complex is recovered almost quantitatively (92%). When PdCl₂(PPh₃)₂ or PdCl(COOMe)(PPh₃)₂ are used as catalyst precursors for the carbonylation of 1-hexene in MeOH, in the absence of added PPh₃ and in the presence of NEt₃ or of carboxylic acid anions (both of them are known to favor the formation of the carbomethoxy complex), no catalytic activity is observed and the precursors are recovered as palladium(0)carbonylphosphine complexes, ultimately mixed with the carbomethoxy complex.
The results suppport the view that, of the two commonly accepted mechanisms for the catalytic hydrocarbalkoxylation of olefins, involving MH or MCOOR′ addition to the olefinic double bond, only the first one, in which a key intermediate is a Pd-acyl species, is probably involved.
When n-BuOH is isued as solvent the catalytic activity remains high even after 5–6 reuses of the catalyst, whereas in MeOH the activity falls significantly below its initial value because of decomposition of the catalyst into inactive palladium(0) complexes and palladium metal, probably via a carbomethoxypalladium complex.
Carbon monoxide as a building block for organic synthesis. Part I. Highly regioselective alkoxycarbonylation of allylbenzene catalyzed by palladium complexes
1990, Journal of Molecular Catalysis
The various parameters governing the alkoxycarbonylation of 3-phenylpropene were investigated in order to select an efficient catalytic system for the conversion of various naturally-occurring allylbenzenes into the corresponding esters. The complex PdCl₂(PPh₃)_2, in the presence of a slight excess of phosphine and SnCl₂·2H₂O catalyzed this reaction at 4 MPa, with a good selectivity and a regioselectivity in linear ester as high as 95%. Several diphosphine ligands were conveniently used, and in many cases the regioselectivity was controlled by the reaction conditions.
The cobalt-catalyzed hydroesterification of acrylonitrile
1983, Journal of Molecular Catalysis
The hydroesterification of acrylonitrile with carbon monoxide and methanol in the presence of hydrogen has been investigated using novel base-promoted cobalt catalyst systems at pressures between 200 – 1000 psig and temperatures between 75 – 125 °C. The reaction affords high yields of methyl 3-cyanopropionate and/or methyl 2-cyanopropionate. The relative distribution of the two isomers can be dramatically controlled by the appro- priate choice of base promoter and process conditions. High selectivity (92%) to methyl 2-cyanopropionate, has been obtained using certain diamine (e.g., N,N,N',N'-tetramethylpropanediamine) promoted catalyst systems. Methyl 3-cyanopropionate, has been obtained selectively using certain pyridine-N-oxide (e.g., 4-picoline-N-oxide) promoted catalysts. However, these latter systems tend to degrade during the course of the reaction. Both the rate of the reaction and the selectivity are markedly affected by changes in the steric and electronic properties of the base promoter, the solvent, temperature, pressure, the amount of H₂ and other process variables.

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Metals in organic syntheses I. Propene hydrocarboxylation with various alkanols and PdCl2(PPh3)2 as catalyst precursor

Abstract

Justus Liebigs Ann. Chem.

U.S. Pat.

Chem. Abstr.

Angew. Chem.

Justus Liebigs Ann. Chem.

Chem. Rev.

Tetrahedron Lett.

Chem. Rev.

Angew. Chem. Int. Ed. Engl.

J. Org. Chem.

J. Org. Chem.

Chem. Ind. (London)

Metals in organic syntheses I. Propene hydrocarboxylation with various alkanols and PdCl₂(PPh₃)₂ as catalyst precursor