Rapid Access to Fused Tetracyclic N-Heterocycles via Amino-to-Alkyl 1,5-Palladium Migration Coupled with Intramolecular C(sp<sup>3</sup>)–C(sp<sup>2</sup>) Coupling

Chen, Dianpeng; Li, Jianming; Zhang, Xiuhua; Liu, Gongle; Wang, Xin; Liu, Yongwei; Liu, Xuan; Shan, Yingying

doi:10.1021/acs.orglett.3c02034

Cited by 4 publications

(2 citation statements)

References 67 publications

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“…Recently, Chen and Shan demonstrated an unprecedented cascade cyclization of isocyanides 69 with alkyne-tethered aryl iodides 70, in which an amino-to-alkyl 1,5-palladium migration was described for the first time. [26] A range of fused tetracyclic N-heterocyclic product 71 could be prepared up to 86 % yield (Scheme 17a). Similar to previous studies, the authors also perform deuterium-labelled experiment.…”

Section: Amino-to-alkyl Migrationmentioning

confidence: 99%

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Fang,

Ding,

Huang

2024

ChemCatChem

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“Through space” metal/hydrogen shift constitutes one of the efficient elementary step in organometallic chemistry to achieve selective remote C‐H bond functionalization. Compared with the relatively extensive exploration on 1,4‐palladium migration, the processes on corresponding 1,5‐palladium translocation are far less explored. Based on our understanding on related research areas, we summarized the advances achieved on remote C‐H bond activation through a key step of 1,5‐palladium migration in this minireview. The background, reaction scope, and more importantly, the mechanistic rationale of each transformation was discussed. We hope by reading through this minireview, one could get a general perspective on direct C‐H bond activation via 1,5‐palladium/hydrogen shift, and could understand why such a process is less common when compared with the process going through 1,4‐palladium/hydrogen migration, and eventually could be inspired to develop practical ways for the synthesis of valuable molecules, which could not be prepared easily through other traditional approach.

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Section: Amino-to-alkyl Migrationmentioning

confidence: 99%

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Fang,

Ding,

Huang

2024

ChemCatChem

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“…In the past decades, Pd-catalyzed isocyanide insertion reactions have witnessed rapid development . In this aspect, a strategy of functionalized isocyanide was successfully developed and applied for the construction of a variety of N -heterocycles .…”

mentioning

confidence: 99%

Electrophile-Controlled Regiodivergent Palladium-Catalyzed Imidoylative Spirocyclization of Cyclic Alkenes

Ding,

Pu,

Lin

et al. 2024

Org. Lett.

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An intermolecular controllable Pd-catalyzed spirocyclization of isocyano cycloalkenes has been developed, offering efficient and selective approaches toward spirocyclic hydropyrrole scaffolds. 2-Azaspiro-1,7-dienes could be obtained through a "chain-walking" process with aryl/vinyl iodides as electrophiles, while the normal Heck product 2-azaspiro-1,6-dienes were selectively generated when aryl triflates were used as the coupling partner of isocyanides. Mechanistic studies suggested that the counteranion of the Pd(II) intermediate played a crucial role in the regioselectivity control. Dihydropyrrole-fused 5,6,7-membered spirocycles were switchably accessed under mild conditions with wide functional group tolerance.

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[1,2]‐Phospha‐Brook Rearrangement‐Initiated Palladium‐Catalyzed Cyclization Reaction of Isocyanides and o‐Bromobenzaldehydes: Access to 2H‐Isoindole‐1‐carboxamides and 2H‐Isoindole‐1‐carbonitriles

Wang,

Gao,

Jiang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryHerein, a [1,2]‐phospha‐Brook rearrangement‐initiated palladium‐catalyzed cyclization reaction for base‐controlled selective synthesis of 2H‐isoindole‐1‐carboxamide and 2H‐isoindole‐1‐carbonitrile derivatives has been described. This strategy features double isocyanide insertion, efficient bond combinations, simple operation and reaction conditions. Mechanistic studies show that the [1,2]‐phospha‐Brook rearrangement is the key step in this reaction. This protocol offers a novel and concise strategy for the synthesis of 2H‐isoindole derivatives.

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Rapid Access to Fused Tetracyclic N-Heterocycles via Amino-to-Alkyl 1,5-Palladium Migration Coupled with Intramolecular C(sp³)–C(sp²) Coupling

Cited by 4 publications

References 67 publications

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Electrophile-Controlled Regiodivergent Palladium-Catalyzed Imidoylative Spirocyclization of Cyclic Alkenes

[1,2]‐Phospha‐Brook Rearrangement‐Initiated Palladium‐Catalyzed Cyclization Reaction of Isocyanides and o‐Bromobenzaldehydes: Access to 2H‐Isoindole‐1‐carboxamides and 2H‐Isoindole‐1‐carbonitriles

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Rapid Access to Fused Tetracyclic N-Heterocycles via Amino-to-Alkyl 1,5-Palladium Migration Coupled with Intramolecular C(sp3)–C(sp2) Coupling

Cited by 4 publications

References 67 publications

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Taming the Selective C−H Bond Activation through 1,5‐Palladium Migration

Electrophile-Controlled Regiodivergent Palladium-Catalyzed Imidoylative Spirocyclization of Cyclic Alkenes

[1,2]‐Phospha‐Brook Rearrangement‐Initiated Palladium‐Catalyzed Cyclization Reaction of Isocyanides and o‐Bromobenzaldehydes: Access to 2H‐Isoindole‐1‐carboxamides and 2H‐Isoindole‐1‐carbonitriles

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Rapid Access to Fused Tetracyclic N-Heterocycles via Amino-to-Alkyl 1,5-Palladium Migration Coupled with Intramolecular C(sp³)–C(sp²) Coupling