Palladium‐Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid‐Free Conditions: Atom‐Economic Synthesis of β,γ‐Unsaturated Esters

Fang, Xianjie; Li, Haoquan; Jackstell, Ralf; Beller, Matthias

doi:10.1002/anie.201404563

Cited by 43 publications

(33 citation statements)

References 45 publications

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“…Longer reactiontimes of up to 48 ha nd the addition of further amountso fc atalystd id not convert 3 into the desired diester 4.P robably, 3b was formed (Scheme7), which bears ac onjugated double bond at the end of the carbon chain that was unreactiveu nder the given conditions. As uccessfula lkoxycarbonylation of conjugate double bonds was achieved either by using nonacidic conditions with lower ligand/metal ratio [19] or by employing another reactions ystem involving aC O/H 2 mixture.…”

Section: Investigation Of the Reaction Pathwaya Nd Progress Of The Rementioning

confidence: 99%

“…The remaining 30 %o f3b is not lost or aw aste product. Reported examples deal with the alkoxycarbonylation of conjugated dienest og ive unsaturated esters [19] or,m ore interestingly, with at andem sequence of conjugated dienes to give saturated esters [6e] (Scheme 12). An extension of the tandem ether formation/ether carbonylation/methoxycarbonylation with an additional alkoxycarbonylation step could yield the desired unsaturated diester 4 or even the saturated diestero f 4,w hich would be equally desirable.…”

Section: Investigation Of the Reaction Pathwaya Nd Progress Of The Rementioning

confidence: 99%

“…Scheme12. Alkoxycarbonylation of conjugated double bondst og ive unsaturated [19] and saturated [6e] ester.…”

Section: Applying Other Ligands Under Similar Conditionsmentioning

confidence: 99%

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Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Ostrowski

Vogelsang

Seidensticker

et al. 2015

Chemistry A European J

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A new tandem catalytic process was designed and developed as a tool for the direct conversion of the widely available feedstock 2,7-octadienol into an α,ω-diester. This innovative auto-tandem catalysis is atom efficient and consists of three consecutive palladium-catalysed reactions: ether formation, ether carbonylation and alkoxycarbonylation. By using the design of experiments (DoE) approach, significant parameters were determined and the yield of the desired α,ω-diester was optimised. Model substrates allowed deeper insight into the progress of the reaction to be gained and, as a result, the reaction sequence was uncovered. Furthermore, by simply applying other ligands, a different reaction path was followed, allowing other, new tandem catalytic sequences to be explored and enabling new compounds to be obtained.

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Section: Investigation Of the Reaction Pathwaya Nd Progress Of The Rementioning

confidence: 99%

Section: Investigation Of the Reaction Pathwaya Nd Progress Of The Rementioning

confidence: 99%

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Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Ostrowski

Vogelsang

Seidensticker

et al. 2015

Chemistry A European J

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“…[1][2][3][4] Especially the field of homogeneous palladium catalysis provides aw ide variety of carbonylation reactions to convert chemicalf eedstocks with several functionalitiesi nto valuable esters for example, terminal olefins, 1,3-dienes and allylic compounds. [5][6][7][8][9] In recent years, the methoxycarbonylation and the carbonylation of allylic compounds have become reactions with high industrial and academic impact. [10][11][12][13] Very recently, the designo fan ew ligand, the 1,2-bis((tert-butyl)pyridine-2yl)phosphanyl)methyl)benzene (py t bpx) set an ew benchmark of ethenec arbonylation competing with the application of the existing 1,2-bis(tert-butyl)phosphanyl)methyl)benzene (1,2-DTBPMB)l igand,w hich allows for extremelyh igh conversion rates in the palladium-catalysed methoxycarbonylation (TOF: 40,000 h À1 )w ith selectivity higher than 99 %o ft he generated esters.…”

Section: Introductionmentioning

confidence: 99%

From Carboxytelomerization of 1,3‐Butadiene to Linear α,ω‐C₁₀‐Diester Combinatoric Approaches for an Efficient Synthetic Route

Vogelsang

Raumann

Hares

et al. 2018

Chemistry A European J

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Two novel reaction pathways were tested to synthesize the linear α,ω-C -diester exclusively from three basic reagents: 1,3-butadiene, carbon monoxide and methanol. Therefore, carboxytelomerization of 1,3-butadiene and methanol was merged with methoxycarbonylation in two different ways to obtain highly linear C -diester. Through a palladium-based and -assisted tandem catalytic system, 22 % yield of the desired C -diester was obtained without isolating the intermediates. Subsequently, the limitations of the novel assisted tandem catalytic concept were uncovered and based on that, a two-step reaction regime was established. By optimization of the carboxytelomerization, the C -monoester as intermediate could be formed in nearly quantitative yields and excellent linearity. In a second reaction step, the isolated monoester was successfully converted by methoxycarbonylation into the desired linear C -diester in overall yields up to 84 %.

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“…Based on our continued interest and experience in carbonylation reactions,w ee nvisioned and started to explore the synthesis of imides from alkenes and amides. [12] Herein, we report an ovel palladium-catalyzed hydroamidocarbonylation of alkenes for the synthesis of various synthetically interesting imides.…”

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confidence: 99%

Palladium‐Catalyzed Hydroamidocarbonylation of Olefins to Imides

Dong

Neumann

et al. 2015

Angewandte Chemie

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Carbonylation reactions allow the efficient synthesis of all kinds of carbonyl-containing compounds.H ere,w e report as traightforwards ynthesis of various imides from olefins and CO for the first time.T he established hydroamidocarbonylation reaction affords imides in good yields (up to 90 %) and with good regioselectivity (up to 99:1) when applying different alkenes and amides.The synthetic potential of the method is highlighted by the synthesis of Aniracetam by intramolecular hydroamidocarbonylation.Carbonylation reactions using carbon monoxide (CO) as one of the cheapest and most flexible C1 building blocks continues to attract significant interest in organic synthesis and from industrial chemists.[1] In terms of production scale, carbonylation reactions nowadays constitute the largest industrial applications in the area of homogeneous catalysis. [2] In addition to the well-known Monsanto [3] or Cativa process [4] which produce acetic acid by the carbonylation of methanol, carbonylative transformations of simple alkenes have been shown to be core processes in industry for the production of esters (alkoxycarbonylation) [5] and aldehydes (hydroformylation).[6] However,t he related synthesis of more value added amides (aminocarbonylations) from simple alkene has been less explored. [7] In this respect, our research group recently reported ag eneral aminocarbonylation of alkenes by using ap alladium catalyst system.[7b] Thea minocarbonylation of various conjugated dienes to synthesize the corresponding b,g-unsaturated amide was also developed.[7d] Notably,a ll these reactions proceed with high atom economy. [8] Apart from amides,i mides also constitute an important organic moiety in fine chemicals.F or example,t etraacetylethylenediamine (TAED) is used on multi-10 000 ton scale as ap eroxide bleach activator in detergents.M oreover,t his functional group is used in the synthesis of pharmaceuticals as well as agrochemicals and various bioactive molecules.A s shown in Scheme 1, selected examples include Diacetazotol (Dermagan), which stimulates wound epithelization, Formothion, asystemic and contact insecticide,T halidomide,which shows antiangiogenic and antineoplastic properties,Pecilocin, with antifungal activity,a nd the anxiolytic drug Aniracetam (Ampamet). [9] Ty pical syntheses of imides proceed by the nucleophilic substitution of activated carboxylic acid derivatives,f or example,a cid chlorides or anhydrides,w ith amides in the presence of base under carefully controlled conditions.[10] The selective oxidation of amides to imides is also known in afew cases. [11] Compared to the existing methods,t he direct carbonylation of easily available olefins to imides would be advantageous with respect to waste formation and step economy (100 %atom efficiency). Based on our continued interest and experience in carbonylation reactions,w ee nvisioned and started to explore the synthesis of imides from alkenes and amides.[12] Herein, we report an ovel palladium-catalyzed hydroamidocarbonylation of alken...

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Palladium‐Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid‐Free Conditions: Atom‐Economic Synthesis of β,γ‐Unsaturated Esters

Cited by 43 publications

References 45 publications

Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

From Carboxytelomerization of 1,3‐Butadiene to Linear α,ω‐C₁₀‐Diester Combinatoric Approaches for an Efficient Synthetic Route

Palladium‐Catalyzed Hydroamidocarbonylation of Olefins to Imides

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Palladium‐Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid‐Free Conditions: Atom‐Economic Synthesis of β,γ‐Unsaturated Esters

Cited by 43 publications

References 45 publications

Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

From Carboxytelomerization of 1,3‐Butadiene to Linear α,ω‐C10‐Diester Combinatoric Approaches for an Efficient Synthetic Route

Palladium‐Catalyzed Hydroamidocarbonylation of Olefins to Imides

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From Carboxytelomerization of 1,3‐Butadiene to Linear α,ω‐C₁₀‐Diester Combinatoric Approaches for an Efficient Synthetic Route