Palladium‐Catalyzed Dearomative<i>syn</i>‐1,4‐Carboamination with Grignard Reagents

Tang, Conghui; Okumura, Mikiko; Zhu, Yunbo; Hooper, Annie R.; Yu, Zhou; Lee, Yu-Hsuan; Šarlah, David

doi:10.1002/anie.201905021

Cited by 43 publications

(22 citation statements)

References 97 publications

(47 reference statements)

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“…In 2019, a protocol involving the key excited complex of arenes and MTAD for palladium-catalyzed dearomative functionalization of simple, nonactivated arenes with Grignard reagents was established (Scheme 59). 105 Followed the dearomative visible-light induced [4+2] cycloaddition, a palladiumcatalyzed allylic carbonation was engaged with a variety of alkyl-and aryl-Grignard reagents to afford 1,4-carboaminated products. To demonstrate the practical synthetic utility of this protocol, a series of product diversifications were conducted, as well as the concise synthesis of sertraline from simple naphthalene.…”

Section: Direct Photo-activation Of the Reaction Partnersmentioning

confidence: 99%

Visible-light induced dearomatization reactions

et al. 2022

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Section: Direct Photo-activation Of the Reaction Partnersmentioning

confidence: 99%

Visible-light induced dearomatization reactions

et al. 2022

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“…[19] Interestingly, using palladium as a catalyst, we found that the selectivity of the dearomative carboamination with Grignard reagents occurred exclusively with syn-1,4-selectivity. [20] The reaction with benzene proceeded smoothly with a wide variety of aryl, vinyl, and alkyl Grignard reagents, and the scope of the arenes was extended to various monocyclic and polycyclic arenes (Scheme 8A, conditions A and B). The synthetic utility of this process was demonstrated by the preparation of Sertraline (47), [21] one of the most prescribed antidepressants, from naphthalene (Scheme 8B).…”

Section: Transition-metal-catalyzed Dearomative Aminofunctionalizationmentioning

confidence: 99%

Arenophile-Mediated Photochemical Dearomatization of Nonactivated Arenes

Okumura

Šarlah

2020

Chimia

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Aromatic compounds are one of the most abundant classes of organic molecules and find utility as precursors for alicyclic hydrocarbon building blocks. While many established dearomatization reactions are exceptionally powerful, dearomatization with concurrent introduction of functionality, i.e. dearomative functionalization, is still a largely underdeveloped field. This review aims to provide an overview of our recent efforts and progress in the development of dearomative functionalization of simple and nonactivated arenes using arenophile-arene cycloaddition platform. These cycloadducts, formed via a visible-light-mediated [4+2]-photocycloaddition, can be elaborated in situ through olefin chemistry or transition-metal-catalyzed ring-opening with carbon-, nitrogen-, and oxygen-based nucleophiles, providing access to diverse structures with functional and stereochemical complexity. Moreover, the dearomatized products are amenable to further elaborations, which effectively install other functionalities onto the resulting alicyclic carbocycles. The utility of the arenophile-mediated dearomatization methods are also highlighted by the facile syntheses of natural products and bioactive compounds through novel disconnections.

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“…Reduction of an N‐Boc‐protected primary amine with LAH is a well‐applied method to obtain the N‐methyl product. Table presents three recent examples using LAH or LiAlH(OMe) 3 as the reductant for the reduction of carbamates or ureas.…”

Section: N‐methylationmentioning

confidence: 99%

Advances in the Synthesis of Methylated Products through Indirect Approaches

Chen

2019

Adv Synth Catal

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Methylation is a well‐known structural modification in organic and medicinal chemistry. In addition to using conventional methylation reagents for direct methylation, indirect methylation approaches have been also successfully applied, particularly to tackle the isolation difficulty among the methylated product, the unreacted starting material, and the dimethylated by‐product due to the structural similarities between them. This review summarizes recent advances in the synthesis of methylated products through indirect approaches – transforming functionalized intermediates into the methylated products. The indirect methodologies surveyed in this review are useful for chemists to select appropriate methylation strategies, particularly for the challenging synthesis of methylated products at a large scale in drug discovery. Abbreviations: AIBN: azobisisobutyronitrile; Cbz: carbobenzyloxy; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DIBAL: diisobutylaluminium hydride; FA: formic acid; Fmoc: fluorenylmethyloxycarbonyl; KOTMS: potassium trimethylsilanolate; LAH: lithium aluminium hydride; LiHBEt3: lithium triethylborohydride; PC: photocatalyst; PMHS: polymethylhydrosiloxane; PSMS: zinc bis(phenylsulfonylmethanesulfinate); SAM: S‐adenosylmethionine; SET: single electron transfer; TBAF: tetra‐n‐butylammonium fluoride; TBS: tert‐butyldimethylsilyl; TEA: trimethylamine; TFA: trifluoroacetic acid; TMS: trimethylsilyl; Ts: 4‐toluenesulfonyl.

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Palladium‐Catalyzed Dearomativesyn‐1,4‐Carboamination with Grignard Reagents

Cited by 43 publications

References 97 publications

Visible-light induced dearomatization reactions

Visible-light induced dearomatization reactions

Arenophile-Mediated Photochemical Dearomatization of Nonactivated Arenes

Advances in the Synthesis of Methylated Products through Indirect Approaches

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