Nickel-catalyzed carbonylative cycloaddition of allyl halides and alkenes

Moral, Daniel del; Moretó, Josep M.; Molins, Elı́es; Ricart, Susagna

doi:10.1016/j.tetlet.2008.09.040

Cited by 9 publications

(2 citation statements)

References 21 publications

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“…Because, in a few very slow reactions, we isolated the carbonylative cycloadduct from the reaction of the allyl bromide with itself, we performed the reaction in the absence of acetylene and a good yield of the cycloadduct 9 was obtained (Table 2, entry 17). Although activated olefins like norbornene or norbonadiene are also suitable substrates for the reaction,9 this is the first case of the reaction of a plain olefin. Presumably, the 1,5‐hexadiene is generated independently from the allyl bromide with an excess of iron32 and subsequently treated with the nickel–allyl active species to give the final compound 9 with high stereoselectivity (only one of the two possible stereoisomers is isolated after the final work‐up).…”

Section: Resultsmentioning

confidence: 95%

“…Bearing these facts in mind, we explored new conditions in an effort to make the process catalytic and to find a cheap and stable source of mediator that would allow its practical use. This was achieved by the use of iron in the form of a powder8 and, three years later, the reaction was applied to strained olefins9 to construct, in both cases, the cyclopentane skeleton.…”

Section: Introductionmentioning

confidence: 99%

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The Nickel‐Catalyzed Carbonylative Cycloaddition of Allyl Halides and Acetylenes: An Efficient Tool for Cyclopentane Annelation

Moral

Ricart

Moretó

2010

Chemistry A European J

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From a practical synthetic point of view, the nickel-mediated carbonylative cycloaddition of alkynes and allyl halides is a straightforward method for obtaining the cyclopentane skeleton in high yields and with controlled stereochemistry, especially when considering the efficiency of the intermolecular version of the reaction. The efforts to make the previously stoichiometric process catalytic in nickel, after experimental mechanistic observations, are reported herein. The unexpected intervention of iron as a reductant and the isolation of a final dimeric species that exhibits interesting tautomeric behavior are also presented. An extension of the reaction to new substrates has led to the conclusion that, although the steric and electronic effects of the alkyne substituents are generally irrelevant in relation to the adducts and their yields, those of the allylic counterpart may have a significant influence on the outcome of the reaction. However, the presence of the amine moiety in the alkyne completely inhibited the reaction. The feasibility of a multicentered reaction was verified with a triacetylene in which up to 12 bonds were created at once and in good yield.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

The Nickel‐Catalyzed Carbonylative Cycloaddition of Allyl Halides and Acetylenes: An Efficient Tool for Cyclopentane Annelation

Moral

Ricart

Moretó

2010

Chemistry A European J

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carbonylative cycloaddition

Crosby¹

2020

Catalysis From a to Z

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Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

et al. 2017

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The nickel(0)-catalyzed carbonylative cycloaddition of 1,5-and 1,6-ene-imines with carbon monoxide (CO) is reported. Keytothis reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO) 3 L].Avariety of tri-and tetracyclic g-lactams were thus prepared in excellent yields with 100 % atom efficiency.Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic g-lactams.

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Nickel-catalyzed carbonylative cycloaddition of allyl halides and alkenes

Cited by 9 publications

References 21 publications

The Nickel‐Catalyzed Carbonylative Cycloaddition of Allyl Halides and Acetylenes: An Efficient Tool for Cyclopentane Annelation

The Nickel‐Catalyzed Carbonylative Cycloaddition of Allyl Halides and Acetylenes: An Efficient Tool for Cyclopentane Annelation

carbonylative cycloaddition

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

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