Use of carbon dioxide in chemical syntheses via a lactone intermediate

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

“…A palladium catalyst immobilized on a phosphine-decorated polystyrene polymer [127] or on silica also proved to be active [128]. [24] selectivities of up to 47% for the d-lactone were reported. As a result of the appended nitrile, the reactions could now be run under neat conditions [129].…”

“…The telomerization of 1,3-butadiene with carbon dioxide can yield the five-membered ring lactones and the six-membered ring d-lactone (E)-3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (Scheme 19). The latter lactone can be further converted into a wide range of different products, a topic that has been recently reviewed by Behr [24]. The telomerization with carbon dioxide was first reported by the groups of Inoue [119] and Musco [120].…”

“…The examples of the telomerization of phenolic substrates are therefore relevant and have also been included. Carbon dioxide can also be used as a renewable nucleophile for the production of d-lactones, versatile building blocks that can be further converted to many other products, a topic which has recently been reviewed [24]. This telomerization reaction is currently one of the few processes that make direct use of this abundant renewable substrate into valuable chemicals.…”

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

“…Due to its particular relevance for a potential industrial CO 2 application (butadiene is a large-scale industrial C 4 building block), the δ-lactone was studied further in reactions aiming at its conversion into other value-added products (e.g., hydrogenation, epoxidation, and others) [32] and was investigated in polymerization reactions as a monomer building block [33][34][35]. In particular, radical polymerizations involving the δ-lactone have very recently rekindled interest in the palladiumcatalyzed telomerization of butadiene and CO 2 [34].…”

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

“…[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. 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 reaction, protonation and ß-hydride eliminationc an lead to 6.A lternatively,i ntramolecular ring closure of complex 7 yields either five-or six-membered lactones 1-3,w hich are convertible into each other.M oreover, ß-hydride eliminationf rom 7 and subsequent telomerization can form 4 andr elated isomers.Despite all these works, still Pd(acac) 2 /tricyclohexylphosphine is still considered to be the best catalyst system for this transformation,a lthoughw ith relatively low catalystt urnover numbers (up to 350) and yields up to 45 %( Scheme 2). [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.…”