Decarboxylative reactions with and without light – a comparison

Schwarz, Johanna; König, Burkhard

doi:10.1039/c7gc02949g

Cited by 365 publications

(158 citation statements)

References 458 publications

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“…[1] Inspired by the intriguing efficiency of enzymatic decarboxylation, [2] recent years have seen an upsurge in developing new decarboxylative functionalization strategies to utilize cheap,stable,and highly prevalent carboxylic acids as versatile building blocks. [3] Elegant work by the groups of Okada, [4] Baran, [5] Aggarwal, [6] Hu, [7] and others [8] has identified N-hydroxyphthalimide-derivedr edox active esters (RAEs) as an efficient activating group for aliphatic carboxylic acids in divergent decarboxylative functionalization reactions by single electron transfer (SET) pathways (Scheme 1a). However,t he adoption of as imilar strategy for aromatic decarboxylation has been limited to borylation thus far (Scheme 1b).…”

Section: Introductionmentioning

confidence: 99%

Visible‐Light‐Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions

et al. 2019

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Despite significant progress in aliphatic decarboxylation, an efficient and general protocol for radical aromatic decarboxylation has lagged far behind. Herein, we describe ag eneral strategy for rapid access to both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters followed by their successive use in divergent carbon-heteroatom and carbon-carbon bond-forming reactions.I dentification of as uitable activator for carboxylic acids is the key to bypass ac ompeting single-electrontransfer mechanism and "switcho n" an energy-transfermediated homolysis of unsymmetrical s-bonds for aconcerted fragmentation/decarboxylation process.

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Section: Introductionmentioning

confidence: 99%

Visible‐Light‐Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions

et al. 2019

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“…Carboxylic acids are aw idely available,s tructurally diverse class of molecules.T he decarboxylative conversion of acids into other functional groups is avaluable approach in synthetic chemistry. [1] Owing to the importance of amines in ar ange of applied fields,e ffort has been placed on realizing decarboxylative amination processes [2] that complement C À N bond-forming reactions such as substitutions of organohalides [3] and activated alcohols, [3] and reductive amination of carbonyls. [4] Cu-catalyzed direct oxidative amination under reaction conditions similar to that of the Chan-Evans-Lam reaction [5] has been established for both C(sp)-and C(sp 2 )-carboxylates.…”

Section: Introductionmentioning

confidence: 99%

Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids

et al. 2019

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The decarboxylative coupling of a carboxylic acid with an amine nucleophile provides an alternative to the substitution of traditional organohalide coupling partners. Benzoic and alkynyl acids may be directly aminated by oxidative catalysis. In contrast, methods for intermolecular alkyl carboxylic acid to amine conversion, including amidate rearrangements and photoredox‐promoted approaches, require stoichiometric activation of the acid unit to generate isocyanate or radical intermediates. Reported here is a process for the direct chemoselective decarboxylative amination of electron‐poor arylacetates by oxidative Cu catalysis. The reaction proceeds at (or near) room temperature, uses native carboxylic acid starting materials, and is compatible with protic, electrophilic, and other potentially complicating functionality. Mechanistic studies support a pathway in which ionic decarboxylation of the acid generates a benzylic nucleophile which is aminated in a Chan–Evans–Lam‐type process.

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“…The developed reaction protocols may be transferred to more advanced and custom-designed continuous flow tandem reactors such as the Vapourtec UV-150 module [8,34]. The process furthermore demonstrates the synthesis potential of arylacetic acids [35] as well as photodecarboxylations [36][37][38].…”

Section: Discussionmentioning

confidence: 99%

Continuous Flow Photochemical and Thermal Multi-Step Synthesis of Bioactive 3-Arylmethylene-2,3-Dihydro-1H-Isoindolin-1-Ones

2019

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An effective multi-step continuous flow approach towards N-diaminoalkylated 3-arylmethylene-2,3-dihydro-1H-isoindolin-1-ones, including the local anesthetic compound AL-12, has been realized. Compared to the traditional decoupled batch processes, the combined photochemical-thermal-thermal flow setup rapidly provides the desired target compounds in superior yields and significantly shorter reaction times.Abstract: An effective multi-step continuous flow approach towards N-diaminoalkylated 3arylmethylene-2,3-dihydro-1H-isoindolin-1-ones, including the local anesthetic compound AL-12, has been realized. Compared to the traditional decoupled batch processes, the combined photochemical-thermal-thermal flow setup rapidly provides the desired target compounds in superior yields and significantly shorter reaction times.

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Decarboxylative reactions with and without light – a comparison

Abstract: Carboxylic acids have gained more and more importance as versatile and renewable starting materials for the formation of platform molecules or high-value chemicals.

Cited by 365 publications

References 458 publications

Visible‐Light‐Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions

Visible‐Light‐Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions

Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids

Continuous Flow Photochemical and Thermal Multi-Step Synthesis of Bioactive 3-Arylmethylene-2,3-Dihydro-1H-Isoindolin-1-Ones

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