Selective halogen-lithium exchange in bromophenylalkyl halides

“…[11] The treatment of 2-bromobenzyl bromide (8) with nBuLi also resulted in the self-reaction (Scheme 2c). [12] This reaction provided the dimerized compound 9 in 82% yield. The results can be explained by the nucleophilic substitution of the first generated benzyllithium 10 with another benzyl bromide 8 to provide compound 11, which further reacted with nBuLi to generate organolithium 12.…”

Section: Representative Self-reactions Of Organolithiumsmentioning

confidence: 97%

Trapping of Transient Organolithium Compounds

Inoue

Okano

2020

Asian J Org Chem

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Organolithium chemistry has been widely utilized in organic synthesis as a reliable tool for introducing various functional groups. The intrinsic high reactivity of organolithiums allows rapid chemical transformation; however, the transient organolithiums bearing an electrophilic moiety often cause the undesired reactions such as self-dimerization, isomerization, and decomposition, which prevent further synthetic application. In this minireview, we classify the reactions involving the short-lived organolithiums and focus on the recent progress in flow chemistry, which allows to trap the highly reactive organolithium species. In addition, this review includes other approaches using the related organometallic species that can be performed in a conventional batch reactor. To place the recent development of this field in perspective, the established strategies controlling the reactivities of the short-lived organolithiums provide a shortstep, efficient, and protective group-free synthesis of functionalized organic molecules in medicinal, agrochemical, and material chemistry.

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“…An important side-product in the attempted cyclization of the uncomplexed compounds such as 2-halogenobenzyl bromide or chloride is 9,lO-dihydroanthracene (24), which derives from an intermolecular reaction [35]. Presumably, such processes could be disfavored with Cr(CO), complexes owing to steric hindrance.…”

Section: Attempted Cyclization Of O-substituted Benzylmentioning

confidence: 99%

Organometallic Derivatives of Cycloproparenes

Müller

Bérnardinelli

Jacquier

1992

Helvetica Chimica Acta

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The tricarbonylchromium complex of cyclopropa[b]naphthalene (3a) is deprotonated at C(1) with BuLi. Quenching of the resulting anion with Me1 results in a 1 : 1 mixture of stereoisomeric methyl derivatives 6a and 6b. Peterson olefination of the bis-silylated complex 3b affords the complexed alkylidenecycloproparene 5 in low yield. The tricarbonylchromium complex of cyclopropa [b]anthracene (10) is accessible via bis-hydro-desilylation of 9. Its X-ray structure is also reported. All attempts to synthesize a tricarbonylchromium complex of benzocyclopropene ( l l a ) failed.Introduction. -Transition metals react with cycloproparenes preferentially at one of the cyclopropene C-C bonds or at the C=C bond of the cyclopropene moiety. Attack at the C-C bonds results in formation of metallacyclobutenes, while reaction at the C=C bond leads to metallapropellanes. The preferential mode of the reaction is determined by the substituents at the methylene position of the cycloproparene, the metal, and its ligands.

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Selective halogen-lithium exchange in bromophenylalkyl halides

Cited by 112 publications

References 7 publications

Neocuproine–KOtBu promoted intramolecular cross coupling to approach fused rings

Neocuproine–KOtBu promoted intramolecular cross coupling to approach fused rings

Trapping of Transient Organolithium Compounds

Organometallic Derivatives of Cycloproparenes

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