Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates

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

doi:10.1021/acscatal.9b03461

Cited by 35 publications

(15 citation statements)

References 59 publications

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“…Yamaguchi, Muto, and co-workers developed palladiumcatalyzed three-component coupling reaction of bromoarenes with TMSÀ diazomethane and allyltrifluoroborate to produce dearomatization/allylation products in high yields (Scheme 28). [35] This transformation is considered to proceed through a palladium carbene intermediate, which occurs migratory insertion to generate benzylpalladium intermediate.…”

Section: Formation Of Benzylpalladium Intermediates Via Palladiumà Carbene Migratory Insertionmentioning

confidence: 99%

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: 99%

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Zhang

Feng

Bao

2021

The Chemical Record

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“…1a ) 6 , 14 . Consequently, a high energy barrier is typically encountered, resulting in often harsh conditions for this type of transformations and imposing formidable challenges in controlling regioselectivity and stereoselectivity 15 – 18 . Beyond that, the strong coordination ability of the generated sulfur-containing product may deactivate the metal catalyst or interfere with stereocontrol by competing for binding, thus representing another important issue to address.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the chiral counter anion might induce asymmetric control in this step, leading to enantioenriched dearomatization product 3 . Notably, in addition to the inevitable remote enantiocontrol, this process will encounter other challenges, including regiocontrol on the nucleophilic sites and control over the double bond Z/E -configuration 18 . Product side reactions, such as rearomatization 21 , could provide chemoselectivity challenges.…”

Section: Introductionmentioning

confidence: 99%

Organocatalytic enantioselective dearomatization of thiophenes by 1,10-conjugate addition of indole imine methides

Duan

et al. 2021

Nat Commun

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Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of diverse chiral cyclic molecules from cheap and easily available arenes. This work reports an organocatalytic enantioselective dearomatization of substituted thiophenes in the context of a rare remote asymmetric 1,10-conjugate addition. By suitable stabilization of the thiophenyl carbocation with an indole motif in the form of indole imine methide, excellent remote chemo-, regio-, and stereocontrol in the nucleophilic addition can be achieved with chiral phosphoric acid catalysis under mild conditions. This protocol can be successfully extended to the asymmetric dearomatization of other heteroarenes including selenophenes and furans. Control experiments and DFT calculations demonstrate a possible pathway in which hydrogen bonding plays an important role in selectivity control.

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“…The generation of palladium π-benzyl complexes as catalytic intermediates and their participation in dearomative functionalization is well known in two-component systems. 40 Recently, Muto, Yamaguchi and co-workers 41 described a pioneering dearomative three-component reaction of bromoarenes with TMS-diazomethane and allyl borates. The key feature of this assembling reaction is the use of a diazo compound to generate a Pd-π-benzyl intermediate through a Pd-carbene species.…”

Section: Dearomative Mcrs Of Arenesmentioning

confidence: 99%

Sequential and direct multicomponent reaction (MCR)-based dearomatization strategies

et al. 2020

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Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates

Cited by 35 publications

References 59 publications

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Palladium‐Catalyzed Three‐Component Coupling Reaction via Benzylpalladium Intermediate

Organocatalytic enantioselective dearomatization of thiophenes by 1,10-conjugate addition of indole imine methides

Sequential and direct multicomponent reaction (MCR)-based dearomatization strategies

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