Rh<sup>I</sup>‐Catalyzed P<sup>III</sup>‐Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide

Zhang, Zhuan; Roisnel, Thierry; Dixneuf, Pierre H.; Soulé, Jean‐François

doi:10.1002/ange.201906913

Cited by 17 publications

(3 citation statements)

References 85 publications

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“…[67,68] Nevertheless,1 -decene,1dodecene,1 -tetradecene,a nd even 1-hexadecene led to the corresponding acids in greater than 95 %y ield ( After demonstrating the viability of our system for industrial aliphatic olefins,wewere interested in the hydroxycarbonylation of aromatic and functionalized alkenes,w hich are of interest for fine chemicals,s pecialties,a nd organic synthesis ( Table 3). [69][70][71][72][73][74][75] As an example,s tyrene (1y)w as completely converted with 83 %r egioselectivity towards 3phenyl propionic acid (2y;e ntry 1). By employing allyl benzene (1z)and 4-phenyl-1-butene (1a' '), the corresponding products 2z-a' ' were afforded again in excellent (99 %) yields ( Table 3, entries 2a nd 3).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

et al. 2019

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The synthesis of carboxylica cids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers,c osmetics, pharmaceuticals,a grochemicals,a nd other manufactured chemicals.A lthough hydroxycarbonylations of olefins have been knownf or more than 60 years,c urrently knownc atalyst systems for this transformation do not fulfill industrial requirements,for example,stability.Presented herein for the first time is an aqueous-phase protocol that allows conversion of various olefins,including sterically hindered and demanding tetra-, tri-, and 1,1-disubstituted systems,aswell as terminal alkenes,into the corresponding carboxylic acids in excellent yields.T he outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key-tosuccess is the use of abuilt-in-base ligand under acidic aqueous conditions.This catalytic system is expected to provide abasis for new cost-competitive processes for the industrial production of carboxylic acids.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

et al. 2019

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“…After demonstrating the viability of our system for industrial aliphatic olefins, we were interested in the hydroxycarbonylation of aromatic and functionalized alkenes, which are of interest for fine chemicals, specialties, and organic synthesis (Table 3). [69][70][71][72][73][74][75] As an example, styrene (1 y) was completely converted with 83 % regioselectivity towards 3phenyl propionic acid (2 y; entry 1). By employing allyl benzene (1 z) and 4-phenyl-1-butene (1 a'), the corresponding products 2 z-a' were afforded again in excellent (99 %) yields (Table 3, entries 2 and 3).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

et al. 2019

View full text Add to dashboard Cite

The synthesis of carboxylic acids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers, cosmetics, pharmaceuticals, agrochemicals, and other manufactured chemicals. Although hydroxycarbonylations of olefins have been known for more than 60 years, currently known catalyst systems for this transformation do not fulfill industrial requirements, for example, stability. Presented herein for the first time is an aqueous‐phase protocol that allows conversion of various olefins, including sterically hindered and demanding tetra‐, tri‐, and 1,1‐disubstituted systems, as well as terminal alkenes, into the corresponding carboxylic acids in excellent yields. The outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key‐to‐success is the use of a built‐in‐base ligand under acidic aqueous conditions. This catalytic system is expected to provide a basis for new cost‐competitive processes for the industrial production of carboxylic acids.

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“…Very recently, SoulØ andc o-workers disclosed aR h I -catalyzed P III -directed CÀHb ond alkylations en route to al ibrary of phosphinesw ith pendant alkyl groups (Scheme 9). [18] Initially, the phosphine was reacted with first olefin in presence of potassium acetate and rhodiumc atalyst in toluene at 160 8Cf or 24 h. Thereafter,t he second olefin was introduced, which ultimately Scheme7.Controle xperiments.…”

Section: Rhodium-catalyzed Unsymmetrical Difunctionalizationmentioning

confidence: 99%

Recent Advancements in Transition‐Metal‐Catalyzed One‐Pot Twofold Unsymmetrical Difunctionalization of Arenes

Mandal

Dana

Chowdhury

et al. 2019

Chemistry An Asian Journal

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Transition‐metal‐catalyzed direct C−H bond activation reactions have been embraced as a powerful synthetic tool to access diverse functionalized arenes. However, site‐selective incorporation of multiple distinct functionalities in an arene has always been a formidable challenge. Recent efforts from the synthetic community have disclosed a few dynamic synthetic approaches to fabricate multifunctionalized arenes in one‐pot using a single catalytic system. These reports manifested the immense potential of such approaches to expedite contemporary organic synthesis towards building molecular complexity. In this minireview, we have illustrated the recent progress in this area, highlighting the contribution from several synthetic chemists including our group.

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Rh^I‐Catalyzed P^III‐Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide

Cited by 17 publications

References 85 publications

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Recent Advancements in Transition‐Metal‐Catalyzed One‐Pot Twofold Unsymmetrical Difunctionalization of Arenes

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RhI‐Catalyzed PIII‐Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide

Cited by 17 publications

References 85 publications

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

Recent Advancements in Transition‐Metal‐Catalyzed One‐Pot Twofold Unsymmetrical Difunctionalization of Arenes

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Rh^I‐Catalyzed P^III‐Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide