Carbonylative [5 + 1] Cycloaddition of Cyclopropyl Imines Catalyzed by Ruthenium Carbonyl Complex

Kamitani, Akihito; Chatani, Naoto; Morimoto, Tsumoru; Murai, Shinji

doi:10.1021/jo000795s

Cited by 60 publications

(15 citation statements)

References 16 publications

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“…Cyclopropyl imine substrate 17 undergoes a catalytic rearrangement with 1 to form acyclic α,β-unsaturated product 18 (Figure ). This result suggests that following cyclopropane ring-opening, β-hydride elimination outcompetes the C–N reductive elimination that would lead to 2,5-dihydro-1 H -pyrrole formation. Similarly, cyclopropylcarboxaldehyde 19 undergoes a catalytic rearrangement to form crotonaldehyde 20 in 80% yield .…”

Section: Resultsmentioning

confidence: 99%

Dinuclear Pathways for the Activation of Strained Three-Membered Rings

2018

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Dinuclear, strain-induced ring-opening reactions of vinylaziridines and vinylcyclopropanes are described. The previously reported [NDI]Ni2(C6H6) complex (NDI = naphthyridine–diimine) reacts with N-tosyl-2-vinylaziridine via C–N oxidative addition to generate a dinickel metallacyclic product. On the basis of this stoichiometric reactivity, the [NDI]Ni2(C6H6) complex is shown to be a highly active catalyst for the rearrangement of vinylcyclopropane to cyclopentene. Notably, 2-phenyl-1-vinylcyclopropane undergoes regioselective activation at the less hindered C–C bond in contrast to the noncatalytic thermal rearrangement. DFT calculations provide insight into the ability of the Ni–Ni bond to stabilize key intermediates and transition states along the catalytic pathway.

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Section: Resultsmentioning

confidence: 99%

Dinuclear Pathways for the Activation of Strained Three-Membered Rings

2018

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“…[7] However, catalytic applications have been limited due to the poor coordination ability of cyclopropanes. [8] Therefore, cyclopropyl compounds with an unsaturated bond that can coordinate to a low valent transition metal, such as methylenecyclopropanes, [9] vinylcyclopropanes, [10] cyclopropyl ketones, [11] cyclopropyl imines, [12] and allenylcyclopropanes [13] have been employed as substrates in transition-metal-catalyzed transformations that include ring-opening reactions of the cyclopropyl ring as a key reaction step.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Six‐Membered Oxa‐Nickelacycles: A Ring‐Opening Reaction of Cyclopropyl Ketones

Tamaki

Nagata

Ohashi

2009

Chemistry A European J

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Cyclopropanecarboxaldehyde (1 a), cyclopropyl methyl ketone (1 b), and cyclopropyl phenyl ketone (1 c) were reacted with [Ni(cod)(2)] (cod = 1,5-cyclooctadiene) and PBu(3) at 100 degrees C to give eta(2)-enonenickel complexes (2 a-c). In the presence of PCy(3) (Cy = cyclohexyl), 1 a and 1 b reacted with [Ni(cod)(2)] to give the corresponding mu-eta(2):eta(1)-enonenickel complexes (3 a, 3 b). However, the reaction of 1 c under the same reaction conditions gave a mixture of 3 c and cyclopentane derivatives (4 c, 4 c'), that is, a [3+2] cycloaddition product of 1 c with (E)-1-phenylbut-2-en-1-one, an isomer of 1 c. In the presence of a catalytic amount of [Ni(cod)(2)] and PCy(3), [3+2] homo-cycloaddition proceeded to give a mixture of 4 c (76%) and 4 c' (17%). At room temperature, a possible intermediate, 6 c, was observed and isolated by reprecipitation at -20 degrees C. In the presence of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr), both 1 a and 1 c rapidly underwent oxidative addition to nickel(0) to give the corresponding six-membered oxa-nickelacycles (6 ai, 6 ci). On the other hand, 1 b reacted with nickel(0) to give the corresponding mu-eta(2):eta(1)-enonenickel complex (3 bi). The molecular structures of 6 ai and 6 ci were confirmed by X-ray crystallography. The molecular structure of 6 ai shows a dimeric eta(1)-nickelenolate structure. However, the molecular structure of 6 ci shows a monomeric eta(1)-nickelenolate structure, and the nickel(II) 14-electron center is regarded as having "an unusual T-shaped planar" coordination geometry. The insertion of enones into monomeric eta(1)-nickelenolate complexes 6 c and 6 ci occurred at room temperature to generate eta(3)-oxa-allylnickel complexes (8, 9), whereas insertion into dimeric eta(1)-nickelenolate complex 6 ai did not take place. The diastereoselectivity of the insertion of an enone into 6 c having PCy(3) as a ligand differs from that into 6 ci having IPr as a ligand. In addition, the stereochemistry of eta(3)-oxa-allylnickel complexes having IPr as a ligand is retained during reductive elimination to yield the corresponding [3+2] cycloaddition product, which is consistent with the diastereoselectivity observed in Ni(0)/IPr-catalyzed [3+2] cycloaddition reactions of cyclopropyl ketones with enones. In contrast, reductive elimination from the eta(3)-oxa-allylnickel having PCy(3) as a ligand proceeds with inversion of stereochemistry. This is probably due to rapid isomerization between syn and anti isomers prior to reductive elimination.

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“…The reaction proceeds through coordination of the catalyst to the oxygen atom of 492, attack of the isocyanide on the -carbon of 495, and the intramolecular cyclization of 496.Knight et al reported that the palladium-catalyzed decarboxylative carbonylation of amino acid-derived 5-vinyloxzolidin-2-ones 497 gave the corresponding δ-lactams, 3,6-dihydro-1H-pyridin-2-ones 498, in good to high yields (Scheme 150) 212. This reaction proceeds through release of carbon dioxide, forming the π-allylpalladium intermediate 499, followed by insertion of CO.Kamatani et al reported that Ru 3 (CO) 12 -catalyzed carbonylative [5 + 1]-cycloaddition of the cyclopropyl imines 500 gave the six-membered unsaturated lactams 501 (Scheme 151) 213. The reaction proceeds through the formation of ruthenacycle 502.…”

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confidence: 99%