Recent Development for Formation of Aromatic Compounds via Metallacyclopentadienes as Metal-Containing Heterocycles

Zhou, Lishan; Shi, Li; Kanno, Ken‐ichiro; Takahashi, Tamotsu

doi:10.3987/rev-09-sr(s)6

Cited by 39 publications

(2 citation statements)

References 55 publications

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“…Metallacyclopentadienes are metal-containing heterocycles, which are considered to be the key intermediates for the formation of aromatic derivatives, particularly in the construction of benzene derivatives from the trimerization of alkynes in the stoichiometric and catalytic reactions [49,50]. The reactions of transition-metal complexes with 1,3-butadiynes provide an important and useful ways approach such type of metal-containing heterocycles.…”

Section: Formation Of Metallacyclopentadienesmentioning

confidence: 99%

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Nizami

Hua

2014

Molecules

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Cycloaddition reactions of alkynes are elegant, atom-efficient transformations for the synthesis of carbo-and heterocycles, mostly aromatic, involving the construction of challenging skeletons of complex molecules. Therefore significant efforts have recently been devoted to the development of novel methodologies, efficient strategies and different catalytic systems to broaden the scope of these reactions. We summarize in this review the recent advances in the cycloaddition reactions of 1,3-butadiynes to provide facile and reliable approaches to various functionalized carbo-and heterocycles.

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Section: Formation Of Metallacyclopentadienesmentioning

confidence: 99%

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Nizami

Hua

2014

Molecules

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“…A metallacyclopentadiene skeleton is widely found not only on mononuclear transition metal complexes but also on di- and trinuclear ones. − Metallacyclopentadiene complexes are key intermediates in many important synthetic reactions, including cyclotrimerization of alkynes, and their reactivity has been intensively investigated. − While the reaction of metallacyclopentadiene complex with alkene often affords cyclohexadiene derivatives, − Paneque, Poveda, and co-workers reported that ethylene inserts into the Ir–C bonds of an iridacyclopentadiene skeleton supported by a Tp Me2 ligand (T pMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) and obtained a hexatrienyl complex by the subsequent β-hydrogen elimination . We also previously reported the insertion of ethylene into a μ–η 4 -ruthenacyclopentadiene skeleton in 2a yielding μ–η 2 :η 4 -hexatrienyl complex 3a (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Skeletal Rearrangement of a μ–η²:η⁴-Hexatrienyl Ligand at a Diruthenium Site via a μ–η⁵-Ruthenacyclohexadienyl Intermediate

Takao,

Taniguchi,

Tsurumaki

2024

Organometallics

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A diruthenium complex containing a μ−η 2 :η 4 -1,4dimethylhexatrienyl ligand, [(Cp*Ru) 2 (μ−η 2 :η 4 -CMe�CH− CH�CMe−CH�CH 2 )(μ-H)] (3a), is coordinatively saturated and did not react with any two-electron donors. Instead, it underwent isomerization above 85 °C to a μ−η 2 :η 4 -2,5dimethylhexatrienyl complex, [(Cp*Ru) 2 (μ−η 2 :η 4 -CH�CMe− CH�CH−CMe�CH 2 )(μ-H)] (4a), in which the methyl substituents on the C 6 moiety migrate from the 1,4-to the 2,5positions. A methyl acrylate substituted complex, [(Cp*Ru) 2 {μ-CMe�CH−CH�CMe−CH�C(H)COOMe}(μ-H)] (3b), was also transformed into [(Cp*Ru) 2 {μ-CH�CMe−CH�CH−CMe�C(H)COOMe}(μ-H)] (4b). The molecular structure of 4b, as well as the reaction using 13 C-labeled ethylene, demonstrated that this skeletal rearrangement involves C�C bond cleavage at the terminal vinyl position followed by the C−C bond formation with the α-carbon atom. DFT calculations at a B3LYP level suggested that this skeletal rearrangement proceeds via a μ−η 5 -ruthenacyclohexadienyl intermediate, [(Cp*Ru) 2 (μ−η 5 -CMeCHCHCMeCH−)(Me)] (C). A related μ−η 5 -ruthenacyclohexadienyl complex possessing a terminal hydride, [(Cp*Ru) 2 (μ−η 5 -CMeCHCHCHCH−)(H)] (6c), was obtained by the thermolysis of an unsubstituted μ−η 2 :η 4 -hexatrienyl complex, [(Cp*Ru) 2 (μ-CH�CH−CH�CH−CH�CH 2 )(μ-H)] (3c). The formation of a stable metallacycle skeleton would promote the C−C bond cleavage, and the subsequent C−C bond formation occurs when it contains a substituent with an αhydrogen atom that can form a stable μ−η 2 :η 4 -hexatrienyl skeleton via the β-hydrogen elimination after C−C bond formation.

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Ruthenium‐Mediated [2 + 2 + 2] Cycloaddition

Yamamoto

2013

Transition‐Metal‐Mediated Aromatic Ring Construction

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Recent Development for Formation of Aromatic Compounds via Metallacyclopentadienes as Metal-Containing Heterocycles

Cited by 39 publications

References 55 publications

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Skeletal Rearrangement of a μ–η²:η⁴-Hexatrienyl Ligand at a Diruthenium Site via a μ–η⁵-Ruthenacyclohexadienyl Intermediate

Ruthenium‐Mediated [2 + 2 + 2] Cycloaddition

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Recent Development for Formation of Aromatic Compounds via Metallacyclopentadienes as Metal-Containing Heterocycles

Cited by 39 publications

References 55 publications

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

Skeletal Rearrangement of a μ–η2:η4-Hexatrienyl Ligand at a Diruthenium Site via a μ–η5-Ruthenacyclohexadienyl Intermediate

Ruthenium‐Mediated [2 + 2 + 2] Cycloaddition

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Skeletal Rearrangement of a μ–η²:η⁴-Hexatrienyl Ligand at a Diruthenium Site via a μ–η⁵-Ruthenacyclohexadienyl Intermediate