Heterodimerization of Olefins: A Highly Promising Strategy for the Selective Synthesis of Functionalized Alkenes

Gooßen, Lukas J.; Rodríguez, Nuria

doi:10.1002/anie.200702936

Cited by 22 publications

(5 citation statements)

References 39 publications

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“…1 These methods typically operate via protonation-like ("protic") hydrometallation (intermediate B, Scheme 1b) of electron-rich or electron-neutral terminal vinyl arenes, dienes, or strained alkenes with cationic hydrido complexes of transition metals, such as Ni, Pd, Ru, Co, and Fe. 3 Therefore, hydrometallation of electron-deficient alkenes in the presence of electron-rich alkenes is unfeasible. The existing examples of protic hydrometallation of electron-deficient methyl acrylate, which is achieved via coordination-assisted β-metalation (intermediate C, Scheme 1b), lead to regioisomeric mixtures of the headto-head homodimerization products.…”

Section: ■ Introductionmentioning

confidence: 99%

Enhanced Excited-State Hydricity of Pd–H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes

Sarkar,

Ghosh,

Kurandina

et al. 2023

J. Am. Chem. Soc.

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Photoinduced enhancement of hydricity of palladium hydride species enables unprecedented hydride addition-like ("hydridic") hydropalladation of electron-deficient alkenes, which allows for chemoselective head-to-tail cross-hydroalkenylation of electron-deficient and electron-rich alkenes. This mild and general protocol works with a wide range of densely functionalized and complex alkenes. Notably, this approach also allows for highly challenging cross-dimerization of electronically diverse vinyl arenes and heteroarenes.

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Section: ■ Introductionmentioning

confidence: 99%

Enhanced Excited-State Hydricity of Pd–H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes

Sarkar,

Ghosh,

Kurandina

et al. 2023

J. Am. Chem. Soc.

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“…Transition metal complexes were reported to promote cross-dimerization of two alkynes and of alkyne with vinyl compounds to form enynes and dienes, respectively [ 20 , 21 , 22 , 23 , 24 ]. The cross-dimerization of two vinyl compounds has been focused on hydrovinylation of styrene and of olefins containing polar fnctional groups [ 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ]. α,ω-Dienes undergo transition metal–catalyzed intramolecular hydrovinylation, which provides a convenient route to the cycloolefins [ 36 , 37 , 38 , 39 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Ni Complex Chelated by a [2.2]Paracyclophane-Functionalized Diimine Ligand and Its Catalytic Activity for Olefin Oligomerization

2021

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A diimine ligand having two [2.2]paracyclophanyl substituents at the N atoms (L1) was prepared from the reaction of amino[2.2]paracyclophane with acenaphtenequinone. The ligand reacts with NiBr2(dme) (dme: 1,2-dimethoxyethane) to form the dibromonickel complex with (R,R) and (S,S) configuration, NiBr2(L1). The structure of the complex was confirmed by X-ray crystallography. NiBr2(L1) catalyzes oligomerization of ethylene in the presence of methylaluminoxane (MAO) co-catalyst at 10–50 °C to form a mixture of 1- and 2-butenes after 3 h. The reactions for 6 h and 8 h at 25 °C causes further increase of 2-butene formed via isomerization of 1-butene and formation of hexenes. Reaction of 1-hexene catalyzed by NiBr2(L1)–MAO produces 2-hexene via isomerization and C12 and C18 hydrocarbons via oligomerization. Consumption of 1-hexene of the reaction obeys first-order kinetics. The kinetic parameters were obtained to be ΔG≠ = 93.6 kJ mol−1, ΔH≠ = 63.0 kJ mol−1, and ΔS≠ = −112 J mol−1deg−1. NiBr2(L1) catalyzes co-dimerization of ethylene and 1-hexene to form C8 hydrocarbons with higher rate and selectivity than the tetramerization of ethylene.

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“…Codimerization of alkenes is a promising, atom-efficient synthetic method that affords highly substituted alkenes with various functionalities from simple alkenes. − Thus far, Co, − Ni, − ,,− Ru, − Rh, ,,, Pd, − other transition-metal − complexes, and Lewis or Brønsted acids − have been used as catalysts for this r...…”

Section: Introductionmentioning

confidence: 99%

Ruthenacyclopentanes as Intermediates in the Regio- and Stereoselective Linear Codimerization ofN-Vinylamides with Electron-Deficient Alkenes

et al. 2017

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Tricarbonylruthenacyclopentanes were successfully synthesized by in situ reduction of RuCl3 with Zn-Cu/CO in the presence of N-vinylacetamides and electron-deficient alkenes such as ethyl acrylate, dimethyl fumarate, and dimethyl maleate. X-ray crystallography of the ruthenacyclopentanes revealed that the three carbonyl ligands occupied coordination sites facially, and the ruthenacycle moiety was stabilized by coordination with the acetamido oxygen atom. When the ruthenacyclopentanes in toluene or DMA were heated to 130 °C for 24 h, linear codimers of the alkenes were formed in moderate to good yield. Both the ruthenacyclopentane and the RuCl3/Zn-Cu/alcohol system showed catalytic activity for the linear codimerization of alkenes, affording the codimers in good yield. The results of stoichiometric and catalytic reactions revealed that the codimerization can proceed via ruthenacyclopentane intermediates.

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Heterodimerization of Olefins: A Highly Promising Strategy for the Selective Synthesis of Functionalized Alkenes

Cited by 22 publications

References 39 publications

Enhanced Excited-State Hydricity of Pd–H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes

Enhanced Excited-State Hydricity of Pd–H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes

Synthesis of a Ni Complex Chelated by a [2.2]Paracyclophane-Functionalized Diimine Ligand and Its Catalytic Activity for Olefin Oligomerization

Ruthenacyclopentanes as Intermediates in the Regio- and Stereoselective Linear Codimerization ofN-Vinylamides with Electron-Deficient Alkenes

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