Direct ortho Arylation of Anisoles via the Formation of Four-Membered Lithiumcycles/Palladacycles

Xiong, Xiaoyu; Zhu, Ranran; Huang, Lin; Chang, Shuqin; Huang, Jianhui

doi:10.1055/s-0036-1588863

Cited by 6 publications

(2 citation statements)

References 14 publications

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“…The ligand activates the organolithium, and more gelator was therefore required to formulate a stable gel—25% wt/vol of gelator produced a gel in a vial that was stable to air for 30 min. This n -BuLi/TMEDA gel was used for ortho -lithiation of methoxybenzene 31 56 , and trapping with trimethylsilyl chloride giving silane 32 in 60% yield (Fig. 4h ).…”

Section: Resultsmentioning

confidence: 99%

Organogel delivery vehicles for the stabilization of organolithium reagents

et al. 2023

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Organolithium reagents are a vital tool in modern organic chemistry, enabling the synthesis of carbon–carbon bonds. However, due to their high reactivity, low temperatures, inert atmospheres and strictly dried solvents are usually necessary for their use. Here we report an encapsulating method for the stabilization of sensitive organolithium reagents—PhLi, n-BuLi and s-BuLi—in a low-cost hexatriacontane (C36H74) organogel. The use of this technology is showcased in nucleophilic addition reactions under ambient conditions, low-temperature bromine–lithium exchange, ortho-lithiation and C–H functionalization. The gel substantially enhances organolithium stability, allows simple storage, handling and delivery, and enables reproducible reagent portioning. The use of gels as easily divided delivery vehicles for hazardous organometallics has the potential to transform this area of synthetic chemistry, making these powerful reactions safer and more accessible to non-specialist researchers, and enabling the more widespread use of these common synthetic methods.

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Section: Resultsmentioning

confidence: 99%

Organogel delivery vehicles for the stabilization of organolithium reagents

et al. 2023

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“…Almost 40 years later, a similar strategy was implemented by Huang and co-workers for the ortho -arylation of N , N -dimethylaniline using Pd 2 (dba) 3 as the catalyst, with reduced efficiency however. 31b…”

Section: Ortho -Arylation Of Anilinesmentioning

confidence: 99%

Direct Arylation of C(sp2)–H Bonds in Anilines

et al. 2023

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Anilines selectively arylated at their ortho-, meta- or para- positions are useful building blocks in synthesis and have found applications in many areas. The most straightforward method for their synthesis relies on the direct arylation of a C(sp2)-H bond of anilines, an attractive strategy avoiding the prefunctionalization of the starting anilines provided that such arylations proceed with high levels of regioselectivity. Such reactions are presented and discussed, in a comprehensive manner, in this review article, with an emphasis on the regioselectivity of the processes and factors governing both the reactivity and selectivity.

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