Synthetic approaches to 1,4-dicarbonyl compounds

Lemmerer, Miran; Schupp, Manuel; Kaiser, Daniel; Maulide, Nuno

doi:10.1038/s44160-022-00179-1

Cited by 20 publications

(22 citation statements)

References 68 publications

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“…Here, we report the realization of this concept by using (triphenylphosphoranylidene)acetaldehyde (P1) as a commercially available aldehyde to initiate these two mechanistically distinct radical processes (Figure 1c). This approach allows modular access to 1,4dicarbonyls, which are versatile synthetic intermediates and ubiquitous motifs found in natural products, 13 from two electronically differentiated alkene fragments. The mild and practical conditions of visible-light photoredox catalysis enable the rapid assembly of complex molecules with various functional groups, which are otherwise difficult to use with a polar linchpin coupling strategy.…”

Section: ■ Introductionmentioning

confidence: 99%

“…With a single photoredox catalyst (PC), a one-pot sequence involving two different radical addition reactions via the formation of intermediate ylide P2 was established by the stepwise and controllable generation of nucleophilic and electrophilic carbon-centered radicals. This approach allows modular access to 1,4-dicarbonyls, which are versatile synthetic intermediates and ubiquitous motifs found in natural products, from two electronically differentiated alkene fragments. The mild and practical conditions of visible-light photoredox catalysis enable the rapid assembly of complex molecules with various functional groups, which are otherwise difficult to use with a polar linchpin coupling strategy.…”

Section: Introductionmentioning

confidence: 99%

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Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

2023

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Organic molecules that can be connected to multiple substrates by sequential C–C bond formations can be utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on the use of organometallic species as strong carbon nucleophiles to form C–C bonds, which narrows the functional group compatibility. Here, we describe a metal-free, radical-mediated coupling approach using a formyl-stabilized phosphonium ylide as a multifunctional linchpin under visible-light photoredox conditions. The present method uses the ambiphilic character of the phosphonium ylide, which serves as both a nucleophilic and an electrophilic carbon-centered radical source. The stepwise and controllable generation of these radical intermediates allows sequential photocatalysis involving two mechanistically distinct radical additions, both of which are initiated by the same photocatalyst in one pot with high functional group tolerance. The methodology enables a bidirectional assembly of the linchpin with two electronically differentiated alkene fragments and thus offers rapid and modular access to 1,4-dicarbonyl compounds as versatile synthetic intermediates.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

2023

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“…With a single photoredox catalyst (PC), a one-pot sequence involving two different radical addition reactions via the formation of intermediate ylide P2 is established by a stepwise and controllable generation of nucleophilic and electrophilic carbon-centered radicals. This approach allows a modular access to 1,4-dicarbonyls, which are versatile synthetic intermediates and ubiquitous motifs found in natural products, 13 from two electronically differentiated alkene fragments. The mild and practical conditions of visible-light photoredox catalysis enable a rapid assembly of complex molecules with various functional groups which are difficult to apply to the polar linchpin coupling strategy.…”

Section: Introductionmentioning

confidence: 99%

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

Matsumoto

Maeda

Maruoka

2023

Preprint

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Organic molecules which connect themselves with multiple substrates by sequential C−C bond formations can be utilized as linchpin compounds in multicomponent process. While they are useful for rapidly increasing the molecular complexity, most of the reported linchpin coupling methods rely on the use of organometallic species as strong carbon nucleophiles to form C−C bonds, which narrows the functional group compatibility. Here, we describe a metal-free, radical-mediated coupling approach using a formyl-stabilized phosphonium ylide as a multifunctional linchpin under visible-light photoredox conditions. The present method demonstrates an ambiphilic character of the phosphonium ylide, which serves both as a nucleophilic and an electrophilic carbon-centered radical source. The stepwise and controllable generation of these radical intermediates allows sequential photocatalysis involving two mechanistically distinct radical additions, both of which are initiated by the same photocatalyst in one pot with a high functional-group tolerance. The methodology enables a bidirectional assembly of the linchpin with two electronically differentiated alkene fragments and thus offers rapid and modular access to 1,4-dicarbonyl compounds as versatile synthetic intermediates.

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“…1 In addition, they are common skeletons in natural products possessing interesting biological activities. 2 For that reason, several synthetic approaches have been developed for accessing these building blocks, ranging from classical procedures, 3 such as the conjugate addition of acyl anions to Michael acceptors, like the Stetter reaction, 4 the acylation of homoenolate equivalents, 5 the reaction of enolates with α-haloketones, 6 or the oxidative coupling of enolates, 7 to more recent routes involving metal-catalyzed cross-coupling reactions of different carbonyl derivatives, 8 conjugate addition of acyl radicals, 9 carbene insertion into 1,3-dicarbonyls, 10 hydrocarbonylation reactions, 11 as well as different photocatalyzed processes, 12 or the organocatalytic redox isomerization of allylic alcohols. 13…”

mentioning

confidence: 99%

Synthesis of 1,4-ketoaldehydes and 1,4-diketones by Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols

et al. 2023

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Synthetic approaches to 1,4-dicarbonyl compounds

Cited by 20 publications

References 68 publications

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis

Synthesis of 1,4-ketoaldehydes and 1,4-diketones by Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols

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