Organo-di-Lithio Reagents: Cooperative Effect and Synthetic Applications

Zhang, Shaoguang; Zhang, Wen‐Xiong; Xi, Zhenfeng

doi:10.1007/3418_2013_71

Cited by 14 publications

(3 citation statements)

References 91 publications

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“…Structure reports on dilithio organometallic compounds are relatively rare in comparison with monolithio organometallics . Single crystals of 4 were obtained from a solution in diethyl ether at −30 °C.…”

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confidence: 99%

Fluorenylidene-Functionalized Lithium Phosphonium Di- and Triylides

Schröder

2015

Organometallics

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The 9-fluorenylidene phosphorane Me3PFlu (2) is easily accessible by deprotonation of [Me3P+–FluH]Br– (1). Its selective deprotonation in diethyl ether yielded the phosphonium di- and triylides [(Et2O)Li{CH2–PMe2–Flu}]2 (3) and [(Et2O)Li2{(CH2)2PMe–Flu}]2 (4), respectively. Both complexes crystallize as dimers, exhibiting bridging ylidic methylene fragments. Moreover, the fluorenylidene moieties also act as soft ligands in the vicinity of lithium.

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confidence: 99%

Fluorenylidene-Functionalized Lithium Phosphonium Di- and Triylides

Schröder

2015

Organometallics

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“…1,4-Dilithio-1,3-butadienes were predicted by calculation and proven by X-ray crystal structures to favor a double dilithium bridging structure, similar to the aforementioned 1,4-dilithio-2-butenes . Since the end of the 20th century, Xi et al established an efficient synthetic method to prepare 1,4-dilithio-1,3-butadienes and thoroughly investigated their structure and reactivity, including transmetalation, bifunctional nucleophilic attacks, intramolecular reactions, etc. , 1,4-Dilithio-1,3-butadienes have been employed to synthesize a variety of metallacyclopentadienes of main-group metals, transition metals, and rare-earth metals . Moreover, 1,4-dilithio-1,3-butadienes could function as noninnocent ligands and react with low-valent transition-metal complexes, generating planar, nonplanar, or spiro metalla-aromatic compounds …”

Section: 4- and 15-dicarbanion Compoundsmentioning

confidence: 99%

Dicarbanion Compounds: The Bridge between Organometallic Reagents and Mononuclear Heterocycles

Chai

Zhang

2022

Organometallics

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Dicarbanion compounds, namely organo-bi-metallics in which two metal atoms are separated by all-carbon backbones, are of great importance in organometallic chemistry for not only the interest in the structure but also the wide application in synthesis, especially of mononuclear heterocycles. The synthetic methods and reactivities of dicarbanion compounds highly depend on the type of metals as well as the structure of backbones. For metal types, while there are examples of other metals, lithium and magnesium play important roles in the chemistry of dicarbanion compounds. For the backbone structure, different unsaturated bonds in the backbones result in different rigidities and orientations of carbon−metal bonds and thus have a great impact on the reactivity of dicarbanion compounds. Herein, a general review of the preparation, structure, and reactivity of dicarbanion compounds with different metals and backbones are presented, mainly focusing on the dicarbanion compounds that have been or may potentially be employed in mononuclear heterocycle synthesis. Heterocycles mentioned in this review are mostly metallacycles because of the limitation of synthetic methods.

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“…The hybrid C,N-bidentate ligands can bind to copper atoms with an enhanced chelating effect. Following a different path, Xi’s group discovered that 1,4-dilithio 1,3-butadienes (C,C-bidentate ligand) can stabilize reactive organocopper species to a great extent via a cooperative effect [ 30 , 31 ]. In addition, this C,C-bidentate ligand can also be regarded as an analogue of 1,2-diketimine, which turns out to be a special Z-type non-innocent ligand, producing an unprecedented aromatic dicupro-annulenes [ 32 ].…”

Section: Introductionmentioning

confidence: 99%

C,C- and C,N-Chelated Organocopper Compounds

et al. 2021

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Copper-catalyzed and organocopper-involved reactions are of great significance in organic synthesis. To have a deep understanding of the reaction mechanisms, the structural characterizations of organocopper intermediates become indispensable. Meanwhile, the structure-function relationship of organocopper compounds could advance the rational design and development of new Cu-based reactions and organocopper reagents. Compared to the mono-carbonic ligand, the C,N- and C,C-bidentate ligands better stabilize unstable organocopper compounds. Bidentate ligands can chelate to the same copper atom via η2-mode, forming a mono-cupra-cyclic compounds with at least one acute C-Cu-C angle. When the bidentate ligands bind to two copper atoms via η1-mode at each coordinating site, the bimetallic macrocyclic compounds will form nearly linear C-Cu-C angles. The anionic coordinating sites of the bidentate ligand can also bridge two metals via μ2-mode, forming organocopper aggregates with Cu-Cu interactions and organocuprates with contact ion pair structures. The reaction chemistry of some selected organocopper compounds is highlighted, showing their unique structure–reactivity relationships.

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Organo-di-Lithio Reagents: Cooperative Effect and Synthetic Applications

Cited by 14 publications

References 91 publications

Fluorenylidene-Functionalized Lithium Phosphonium Di- and Triylides

Fluorenylidene-Functionalized Lithium Phosphonium Di- and Triylides

Dicarbanion Compounds: The Bridge between Organometallic Reagents and Mononuclear Heterocycles

C,C- and C,N-Chelated Organocopper Compounds

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