Efficient and chemoselective ethene hydromethoxycarbonylation catalysts based on Pd-complexes of heterodiphosphines o-C6H4(CH2PtBu2)(CH2PR2)

Fanjul, Tamara; Eastham, Graham R.; Haddow, Mairi F.; Hamilton, Alexander; Pringle, Paul G.; Orpen, A. Guy; Turner, Tom P. W.; Waugh, Mark

doi:10.1039/c1cy00409c

Cited by 34 publications

(31 citation statements)

References 69 publications

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“…Later, Pringle’s20b group demonstrated that unsymmetrical ligand S (Figure 5) also outperformed its symmetrical analogues in the methoxycarbonylation of ethylene. In this case, the electron‐poorer phosphine also has an extreme steric requirement that favors the formation of MeP 10a.…”

Section: Methodsmentioning

confidence: 99%

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

Holzapfel

Bredenkamp

2015

ChemCatChem

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The methoxycarbonylation reaction provides ar oute to the synthesis of esters from medium-chain alkenes that may be used as fuel supplements. However,t he known productivec atalytic systems are expensive and/or unstablea te levated temperatures. Most of the data availableo nt he methoxycarbonylation of alkenes is derivedf rom ethylene and styrene as substrates. To broaden the scope, we conducted ac omparative study of ar ange of phosphine ligandsu nder comparable conditions fort he methoxycarbonylation of 1-octene. The results demonstrate that anumber of ligand structural motifs facilitate the process effectually.F urthermore, the critical importance of alkene isomerization and the acid/liganda nd Pd/ligand ratios are presented.Carbonylation reactions provide an efficient route to generate av ariety of functionalg roups from CÀCu nsaturation by using readily available carbon monoxidea nd other ancillary reagents.[1] Amongst others, these metal (Pd, Co, Ni, Rh, etc.) [2] catalyzed carbonylation reactions include the syntheses of aldehydes (hydroformylation), [3] carboxylic acids (hydrocarboxylation), [4] and esters (hydromethoxycarbonylation or methoxycarbonylation for short, Scheme 1). [5] Twom echanisms,n amely,P d ÀHa nd PdÀOMe, have been proposed for the methoxycarbonylationr eaction, each with much study and evidencei nits favor.[5b] However,m ost evidence collected thus far indicatesapreference for the PdÀH mechanism, as shown in Scheme 2. [5c,d] Despite the fact that long-chain esters play ac rucial role in the manufacture of lubricants and surfactants [6] and are eligible candidates for petroleum derivatives, these higher-carbonl inear aliphatic esters are typicallyp roduced by furtherm anipulations of the products of the hydroformylation reaction.[7] However,m uch effort is being devotedt oc atalytic methoxycarbonylation with respect to the utilization of renewable resources. [8] As South Africah as no naturals ource of liquid fuel, there is an opportunity and an eed to convert its (Sasol) FischerTropsch medium-chaino lefins into their correspondingm ethyl esters as substitutes for diesel fuels. Althoughanumber of catalytic systemsh ave been developed for the required methoxycarbonylation, industrial implementation with regard to medium-chain alkenes has not yet been realized. In addition to patent protection,t he known catalysts suffer from an umber of disadvantages, includingh igh cost. Most often, these systems comprise Pd 2 (dba) 3 (dba = dibenzylideneacetone)a nd the ligands( andt heir analogues) shown in Figure 1. [8, 9] The use of ligand A in the methoxycarbonylation of ethylene is aw ellknown industrial process (Lucite process).[10i]The requirements for ap otential industrial catalystw ould include low cost, efficiency in terms of reactionr ates and selectivity,h ight emperature stability, and the capability of recycling. The development of ac atalysts ystem of this kind can be expedited by ab etter understanding of the critical factors, in particular, ligand structure and reaction con...

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Section: Methodsmentioning

confidence: 99%

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

Holzapfel

Bredenkamp

2015

ChemCatChem

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“…8,9 It is clear from Fig. 1 and 2 that the z-coordinates of the backbone phenylene group render the CH 2 protons and the t Bu substituents inequivalent in both 1a and 2a.…”

Section: Platinum(ii) and Palladium(ii) Coordination Chemistrymentioning

confidence: 95%

Interplay of bite angle and cone angle effects. A comparison between o-C₆H₄(CH₂PR₂)(PR′₂) and o-C₆H₄(CH₂PR₂)(CH₂PR′₂) as ligands for Pd-catalysed ethene hydromethoxycarbonylation

et al. 2013

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The following unsymmetrical diphosphines have been prepared: o-C6H4(CH2PtBu2)(PR2) where R = PtBu2 (L3a); PCg (L3b); PPh2 (L3c); P(o-C6H4CH3)2 (L3d); P(o-C6H4OCH3)2 (L3e) and o-C6H4(CH2PCg)(PCg) (L3f) where PCg is 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-6-yl. Hydromethoxycarbonylation of ethene under commercially relevant conditions has been investigated in the presence of Pd complexes of each of the ligands L3a–f and the results compared with those obtained with the commercially used o-C6H4(CH2PtBu2)2 (L1a). The Pd complexes of the bulkiest ligands L3a, L3b and L3f are highly active catalysts but the Pd complexes of L3c, L3d and L3e are completely inactive. The crystal structures of the complexes [PtCl2(L1a)] (1a) and [PtCl2(L3a)] (2a) have been determined and show that the crystallographic bite angles and cone angles are greater for L1a than L3a. Solution NMR studies show that the seven-membered chelate in 1a is more rigid than the six-membered chelate in 2a. Treatment of [PtCl(CH3)(cod)] with L3a–f gave [PtCl(CH3)(L3a–f)] as mixtures of 2 isomers 3a–f and 4a–f. The ratio of the products 4:3 ranges from 100:1 to 1:20, the precise proportion is apparently governed by a balance of two competing factors, steric bulk and the antisymbiotic effect. The palladium complexes [PdCl(CH3)(L3b)] (5b/6b) and [PdCl(CH3)(L3c)] (5c/6c) react with labelled 13CO to give the corresponding acyl species [PdCl(13COCH3)(L3b)] (7b/8b) and [PdCl(13COCH3)(L3c)] (7c/8c). Treatment of [PdCl(13COCH3)(L)] with MeOH gave CH3(13)COOMe rapidly when L = L3b but very slowly when L = L3c paralleling the contrasting catalytic activity of the Pd complexes of these two ligands.

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“…111 The field of hydro/methoxycarbonylation of ethylene to methyl propanoate using BTDPMB-based systems and variations of the ligand has been recently reviewed by Fanjul and co-workers. [112][113][114] Drent and Jager have shown the BTDPMB/palladium system to give methyl pentanoate from 2-butene in 97% selectivity at 65 bar and 100℃, 115 showing the methoxycarbonylation of a carbon chain longer than ethylene was possible. The same authors desired to increase the selectivity to the linear ester and found that using a mixture anisole/methanol : 2/1 as a solvent for the methoxycarbonylation of 2-butene and 1-octene yielded a full conversion to the ester with high selectivity to the linear species (97%).…”

Section: The Alkoxycarbonylation Of Simple Alkenesmentioning

confidence: 99%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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Dimethyl 1,19-nonadecanedioate is produced from the methoxycarbonylation of commercial olive, rapeseed or sunflower oils in the presence of a catalyst derived from [Pd 2 (dba) 3 ], bis(ditertiarybutylphosphinomethyl)benzene (BDTBPMB) and methanesulphonic acid (MSA). The diester is then hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-(diphenylphosphinemethyl)ethane (triphos). 1,19-Nonadecadienoic acid is hydrogenated to short chain oligoesters, which can themselves be hydrogenated to 1,19-nonadecanol by hydrogenation in the presence of water.

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Efficient and chemoselective ethene hydromethoxycarbonylation catalysts based on Pd-complexes of heterodiphosphines o-C₆H₄(CH₂P^tBu₂)(CH₂PR₂)

Cited by 34 publications

References 69 publications

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

Interplay of bite angle and cone angle effects. A comparison between o-C₆H₄(CH₂PR₂)(PR′₂) and o-C₆H₄(CH₂PR₂)(CH₂PR′₂) as ligands for Pd-catalysed ethene hydromethoxycarbonylation

Polymer precursors from catalytic reactions of natural oils

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Efficient and chemoselective ethene hydromethoxycarbonylation catalysts based on Pd-complexes of heterodiphosphines o-C6H4(CH2PtBu2)(CH2PR2)

Cited by 34 publications

References 69 publications

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

An Empirical Study of Phosphine Ligands for the Methoxycarbonylation of Medium‐Chain Alkenes

Interplay of bite angle and cone angle effects. A comparison between o-C6H4(CH2PR2)(PR′2) and o-C6H4(CH2PR2)(CH2PR′2) as ligands for Pd-catalysed ethene hydromethoxycarbonylation

Polymer precursors from catalytic reactions of natural oils

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Efficient and chemoselective ethene hydromethoxycarbonylation catalysts based on Pd-complexes of heterodiphosphines o-C₆H₄(CH₂P^tBu₂)(CH₂PR₂)

Interplay of bite angle and cone angle effects. A comparison between o-C₆H₄(CH₂PR₂)(PR′₂) and o-C₆H₄(CH₂PR₂)(CH₂PR′₂) as ligands for Pd-catalysed ethene hydromethoxycarbonylation