A Practical Palladium-Catalyzed Telomerization for the Synthesis of Functionalized Alcohols

Jackstell, Ralf; Grotevendt, Anne; Andreu, Mario Gómez; Beller, Matthias

doi:10.1021/op800278g

Cited by 14 publications

(8 citation statements)

References 77 publications

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“…A yield of 73% was reported for 1,4‐butanediol, which constitutes a selectivity towards the monoether of 75%. In up‐scaling experiments with diols and aminoalcohols for polymer use, this was proven to be a valid approach for industrial use . Furthermore, the reactivities of the Pd/NHC catalysts towards 1,3‐dienes and nucleophiles clearly differ.…”

Section: Catalystsmentioning

confidence: 99%

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

2019

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Telomerization is a versatile tool for synthesizing unsaturated ethers, amines and other molecules starting from 1,3‐dienes and respective nucleophiles. The homogeneously catalyzed reaction has been the subject of academic and industrial research for over 50 years, offering a broad variety of substrates, catalysts and process concepts. This Minireview presents the advances and developments in this field over the last decade. The focus was on the conversion of renewable resources, the synthesis of promising new products and the development of efficient process concepts to combine these.

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Section: Catalystsmentioning

confidence: 99%

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

2019

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“…The catalyst [37], either generated in situ from the corresponding imidazolium salt or the molecularly defined divinyldisiloxane complex [Pd(Imes)(dvds)] (Fig. 3), was used in the telomerization of 1,3-butadiene with methanol [38][39][40]. The N-heterocyclic carbenes are in general better s-donor ligands and come with considerably different steric requirements than the phosphines.…”

Section: Typical Catalysts and Ligands Used In Telomerization Reactionsmentioning

confidence: 99%

“…The group of Beller [39,78] also investigated the telomerization of 1,3-butadiene with ethylene glycol. Several ligands were screened, including IMes, the more sterically demanding carbene L4, PPh 3 and TOMPP, for activity at a Pd concentration of 0.001 mol% (Fig.…”

Section: Telomerization Of Ethylene Glycolmentioning

confidence: 99%

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

Bruijnincx

Jastrzebski

Hausoul

et al. 2012

Organometallics and Renewables

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The dimerization of 1,3-dienes (e.g. butadiene) with the addition of a protic nucleophile (e.g. methanol) yields 2,7-octadienyl ethers in the so-called telomerization reaction. This reaction is most efficiently catalyzed by homogeneous palladium complexes. The field has experienced a renaissance in recent years as many of the platform molecules that can be renewably obtained from biomass are well-suited to act as multifunctional nucleophiles in this reaction. In addition, the process adheres to many of the principles of green chemistry, given that the reaction is 100% atom efficient and produces little waste. The telomerization reaction thus provides a versatile route for the production of valuable bulk and specialty chemicals that are (at least partly) green and renewable. The use of various multifunctional substrates that can be obtained from biomass is covered in this review, as well as mechanistic aspects of the telomerization reaction.

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“…To solve these problemsm ost of the known reactions of carbon dioxide make use of highly reactive substrates and/orn eed harsh reaction conditions, limiting the practical applications of such methods. Based on our long standing interest in telomerization reactions, [28][29][30][31][32] as well as the valorization of carbon dioxide, [1,4,33] we recently started aj oint program to improvet he synthesis of the d-lactone 1 as an intermediate for novel polymers based on carbon dioxide.To develop superior catalytic systems, whicha llow for the synthesis of d-lactone 1 from 1,3-butadiene and carbon dioxide in high yield and selectivity, we studied the influenceo f variousp hosphine ligands (Scheme3;L1-L22)i nt he presence of 0.06 mol %p alladium catalyst (Pd(acac) 2 /L = 1:3). [13][14][15] In contrast to all these reactions vide supra, the catalytic telomerization of 1,3-butadiene with carbon dioxide leads straightforward to the unsaturated d-lactone 1 (3-ethylidene-6-vinyltetrahydro-2Hpyran-2-one) under mild conditions in a1 00 %a tom-efficient manner (Scheme 1).…”

mentioning

confidence: 99%

“…Based on our long standing interest in telomerization reactions, [28][29][30][31][32] as well as the valorization of carbon dioxide, [1,4,33] we recently started aj oint program to improvet he synthesis of the d-lactone 1 as an intermediate for novel polymers based on carbon dioxide. Based on our long standing interest in telomerization reactions, [28][29][30][31][32] as well as the valorization of carbon dioxide, [1,4,33] we recently started aj oint program to improvet he synthesis of the d-lactone 1 as an intermediate for novel polymers based on carbon dioxide.…”

mentioning

confidence: 99%

Efficient and selective Palladium‐catalyzed Telomerization of 1,3‐Butadiene with Carbon Dioxide

et al. 2016

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Am ore efficient telomerization of 1,3-butadienew ith carbon dioxide leadingt ot he valuable d-lactone1( 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) is reported. The key to success is the use of ap alladium/TOMPP-catalyst system (TOMPP = tris-(o-methoxyphenyl)-phosphine), which provided under optimal conditions significantly increased yields of the desired product and improved catalyst turnover numbers(TON = 1500).For the integrationo fn ovel,s ustainable chemical processes, which resourcefully utilize renewable or easily available feedstocks and selectivelyt ransform them into green and safe products,t he use of optimal catalysts is key. [1][2][3] In this respect, carbon dioxidei sc onsidered to be av aluableC 1b uilding block, owing to its abundance, low toxicity, and recyclability. Consequently,t he development of novel catalysts for the valorization of CO 2 has become an urgent and important goal. [2][3][4] However,e fficient utilization of CO 2 for creating CÀCb onds is still problematic, owing to its thermodynamic stability and/or kinetic inertness. To solve these problemsm ost of the known reactions of carbon dioxide make use of highly reactive substrates and/orn eed harsh reaction conditions, limiting the practical applications of such methods. [4][5][6][7][8][9][10][11][12] In particular, creatinge ssential CÀCb onds from CO 2 requires the use of strong carbon nucleophiles, such as organolithiums, Grignardr eagents, and phenolates, which also generate (over)stoichiometric amounts of by-products. [13][14][15] In contrast to all these reactions vide supra, the catalytic telomerization of 1,3-butadiene with carbon dioxide leads straightforward to the unsaturated d-lactone 1 (3-ethylidene-6-vinyltetrahydro-2Hpyran-2-one) under mild conditions in a1 00 %a tom-efficient manner (Scheme 1). Notably,t his palladium-promoted process constitutes also one of the first successful exampleso facatalytic CÀCb ond formation between CO 2 and olefins.P ioneering work in this area wasp erformed by Inoue et al. [16,17] and Musco et al. [18] already in the 1970s. Among the three catalytic systems tested at that time, the combinationo fP d(acac) 2 /tricyclohexylphosphine performed best. Later on, detailed investigations on this catalysts ystem,e ven on miniplant scale, followed by the group of Behr et al. [19][20][21][22][23] Recently,K .N ozaki and coworkers [5] showed that this telomerization reaction can be used as part of environmentally benign co-polymerizations of carbon dioxide and olefins.Meanwhile, severalm echanisms [24,25] for the insertion of CO 2 to 1,3-butadiene to d-lactone 1 have been proposed, [18,[22][23][24][25] including detailed investigationsb yB ehr et al. [26] The generally accepted mechanism shown in Scheme 1 [27] proposes in situgenerated monophosphine-ligated palladium(0) complexes as active catalysts peciesw hich form the crucial h 3 -allyl palladium complex 5.N otably,c omplex 5 contains ah ighly nucleophilic s-Pd-carbon bond, whichi sa ble to insert carbon dioxide to form complex 7.A saside rea...

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A Practical Palladium-Catalyzed Telomerization for the Synthesis of Functionalized Alcohols

Cited by 14 publications

References 77 publications

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

Efficient and selective Palladium‐catalyzed Telomerization of 1,3‐Butadiene with Carbon Dioxide

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