Catalytic three-component C–C bond forming dearomatization of bromoarenes with malonates and diazo compounds

Kato, Hiroki; Musha, Itsuki; Komatsuda, Masaaki; Muto, Kei; Yamaguchi, Junichiro

doi:10.1039/d0sc02881a

Cited by 23 publications

(11 citation statements)

References 64 publications

(6 reference statements)

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“…Very recently, the same group also developed palladiumcatalyzed three-component dearomatization/alkylation reaction of bromoarenes with diazo compounds and malonates to furnish substituted alicyclic products (Scheme 29). [36] Under the optimized conditions, substituted six-membered bromoarenes reacted smoothly to produce 1,4-and 1,2-difunctionalized alicyclic molecules in good to high yields. In addition, the reaction was suitable for a variety of heterocyclic aryl bromides including azines and heteroles.…”

Section: Formation Of Benzylpalladium Intermediates Via Palladiumà Carbene Migratory Insertionmentioning

confidence: 98%

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Zhang

Feng

Bao

2021

The Chemical Record

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Transition-metal catalyzed multi-component reactions have captured the attention of researchers in organic synthesis and drug synthesis due to their advantages of simple operation, easy availability of raw materials and without separation of intermediates. Among the multicomponent reactions, the three-component processes have been developed into effective organic procedures. This personal account reviews our and other group's studies on the development of three-component coupling reaction for the rapid construction of two new chemical bonds simultaneously via benzylpalladium intermediates. Catalyst-switched three-component reactions of benzyl halides, activated olefins, and allyltributylstannane were successfully conducted to produce the corresponding benzylallylation products. Activation and conversion of carbon monoxide and carbon dioxide via π-benzylpalladium intermediates provide access to a wide range of unsaturated ketones and esters with excellent functional group tolerance. Meanwhile, other methods to produce benzylpalladium intermediates, including Heck insertion of alkenes into arylpalladium complexes, the oxidative addition of benzyl carbonate to palladium complexes and palladiumÀ carbene migratory insertion, were also highlighted.

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Section: Formation Of Benzylpalladium Intermediates Via Palladiumà Carbene Migratory Insertionmentioning

confidence: 98%

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Zhang

Feng

Bao

2021

The Chemical Record

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“…Moreover, aryl N ‐tosylhydrazones can be used in the transformation instead of TMS‐diazomethane (Scheme 20). [44] …”

Section: The Formation Of C−c Bonds Via Benzyl Palladium Intermediatementioning

confidence: 99%

Benzyl Palladium Intermediates: Unique and Versatile Reactive Intermediates for Aromatic Functionalization

2020

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Aromatic functionalizations are of current interest and importance in organic chemistry, recent transition‐metal catalyzed reactions can transform inert C−H bond into C−X (X=C, O, N, etc.) bonds, greatly enriching aromatic chemistry and related fields. Some well‐known palladium‐containing intermediates such as palladacycles and allylpalladium intermediates play an important role in organic conversions. Similar with allyl group, benzyl group also possesses the capability of stabilizing palladium through η3‐binding. In the process of the formation of benzyl palladium intermediate, there is a transition state of dearomatization. Therefore, it is a challenging and meaningful research topic to seize these aromatic destruction intermediates, realize selective functionalization reaction on aromatic ring via them, and inhibit the formation of traditional benzylated products. Herein, we summarized the recent efforts on expanding the synthetic utility, as well as exploring the mechanism in aromatic functionalization via reactive benzyl palladium intermediates. We envision that the transformation via benzyl palladium intermediates will help promote the development in the field of palladium–catalyzed aromatic regioselective functionalization.

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“… 16 Then Yamaguchi et al reported the dearomative allylation of benzyl phosphates with allyl borates, 17 as well as a series of beautiful dearomative three component reactions of haloarenes, in which the π-benzyl complex is generated by the Pd-catalyzed insertion of diazo-compounds. 18 Interestingly, nitrogen based as well as malonates and arylacetonitriles based nucleophiles were also reported to support addition to the π-benzyl intermediate, 19,20 although most protocols require subsequent in situ rearomatisation of the formed semibenzene to achieve good conversions. All of these methodologies result in good yields; however, the low reactivity of the reported nucleophiles give rise to longer reaction times (12–24 h) and typically necessitate a relatively high catalyst loading, specific phosphine-ligands and high temperatures.…”

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confidence: 99%

Pd-catalyzed allylative dearomatisation using Grignard reagents

Boldrini

Harutyunyan

2021

Chem. Commun.

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Catalytic three-component C–C bond forming dearomatization of bromoarenes with malonates and diazo compounds

Abstract: A Pd-catalyzed dearomative three-component C–C bond formation of bromoarenes with diazo compounds and malonates was developed. Various bromoarenes ranging from benzenoids to azines and heteroles were transformed to the corresponding...

Cited by 23 publications

References 64 publications

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Benzyl Palladium Intermediates: Unique and Versatile Reactive Intermediates for Aromatic Functionalization

Pd-catalyzed allylative dearomatisation using Grignard reagents

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