A computational study of 1,3-dipolar cycloadditions of nitrile oxides with dienes

Kiss, Lóránd; Escorihuela, Jorge

doi:10.1016/j.tet.2023.133435

Cited by 4 publications

(3 citation statements)

References 81 publications

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“…The 1,3-dipolar cycloaddition of nitrile oxides with cyclodienes leading to cycloalkenefused isoxazolines then converted into dialkenylated heterocycles through ring opening and cross-metathesis was studied at the M06-2X/6-311+G(d,p) level of theory (Scheme 20) [41].…”

Section: Nitrile Oxidesmentioning

confidence: 99%

“…Also, the determined regioselectivity and the formation of the 3,5-isoxazoline confirms the radical mechanism reported in Figure 8. The 1,3-dipolar cycloaddition of nitrile oxides with cyclodienes leading to cycloalkene-fused isoxazolines then converted into dialkenylated heterocycles through ring opening and cross-metathesis was studied at the M06-2X/6-311+G(d,p) level of theory (Scheme 20) [41]. Calculations allowed for locating the different TSs, giving the adduct with the O atom (named a) or the C-atom (named a′) of the isoxazoline closer to the C-sp 2 of the cycloalkene ring.…”

Section: Alkenesmentioning

confidence: 99%

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Density Functional Theory Calculations: A Useful Tool to Investigate Mechanisms of 1,3-Dipolar Cycloaddition Reactions

Chiacchio,

Legnani

2024

IJMS

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The present review contains a representative sampling of mechanistic studies, which have appeared in the literature in the last 5 years, on 1,3-dipolar cycloaddition reactions, using DFT calculations. Attention is focused on the mechanistic insights into 1,3-dipoles of propargyl/allenyl type and allyl type such as aza-ylides, nitrile oxides and azomethyne ylides and nitrones, respectively. The important role played by various metal–chiral–ligand complexes and the use of chiral eductors in promoting the site-, regio-, diastereo- and enatioselectivity of the reaction are also outlined.

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Section: Nitrile Oxidesmentioning

confidence: 99%

Section: Alkenesmentioning

confidence: 99%

Density Functional Theory Calculations: A Useful Tool to Investigate Mechanisms of 1,3-Dipolar Cycloaddition Reactions

Chiacchio,

Legnani

2024

IJMS

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“…Computational studies of [3 + 2] cycloadditions have been carried out to rationalise the reactivity and regioselectivity of these reactions [18][19][20][21][22]. However, these results often contradict the experimentally observed findings [23].…”

Section: Introductionmentioning

confidence: 99%

Spectral Assignment in the [3 + 2] Cycloadditions of Methyl (2E)-3-(Acridin-4-yl)-prop-2-enoate and 4-[(E)-2-Phenylethenyl]acridin with Unstable Nitrile N-Oxides

Maľučká,

Vilková

2024

Molecules

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The investigation of cycloaddition reactions involving acridine-based dipolarophiles revealed distinct regioselectivity patterns influenced mainly by the electronic factor. Specifically, the reactions of methyl-(2E)-3-(acridin-4-yl)-prop-2-enoate and 4-[(1E)-2-phenylethenyl]acridine with unstable benzonitrile N-oxides were studied. For methyl-(2E)-3-(acridin-4-yl)-prop-2-enoate, the formation of two regioisomers favoured the 5-(acridin-4-yl)-4,5-dihydro-1,2-oxazole-4-carboxylates, with remarkable exclusivity in the case of 4-methoxybenzonitrile oxide. Conversely, 4-[(1E)-2-phenylethenyl]acridine displayed reversed regioselectivity, favouring products 4-[3-(substituted phenyl)-5-phenyl-4,5-dihydro-1,2-oxazol-4-yl]acridine. Subsequent hydrolysis of isolated methyl 5-(acridin-4-yl)-3-phenyl-4,5-dihydro-1,2-oxazole-4-carboxylates resulted in the production of carboxylic acids, with nearly complete conversion. During NMR measurements of carboxylic acids in CDCl3, decarboxylation was observed, indicating the formation of a new prochiral carbon centre C-4, further confirmed by a noticeable colour change. Overall, this investigation provides valuable insights into regioselectivity in cycloaddition reactions and subsequent transformations, suggesting potential applications across diverse scientific domains.

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Application of 2‐Azabicyclo[2.2.1]Hept‐5‐En‐3‐One (Vince Lactam) in Synthetic Organic and Medicinal Chemistry

Nonn,

Fustero,

Kiss

2024

The Chemical Record

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Abstract2‐Azabicyclo[2.2.1]hept‐5‐en‐3‐one (Vince lactam) is known to be a valuable building block in synthetic organic chemistry and drug research. It is an important precursor to access of some blockbuster antiviral drugs such as Carbovir or Abacavir as well as other carbocyclic neuraminidase inhibitors as antiviral agents. The ring C=C bond of the Vince lactam allows versatile chemical manipulations to create not only functionalized γ‐lactams, but also γ‐amino acid derivatives with a cyclopentane framework. The aim of the current account is to summarize the chemistry of Vince lactam, its synthetic utility and application in organic and medicinal chemistry over the last decade.

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A computational study of 1,3-dipolar cycloadditions of nitrile oxides with dienes

Cited by 4 publications

References 81 publications

Density Functional Theory Calculations: A Useful Tool to Investigate Mechanisms of 1,3-Dipolar Cycloaddition Reactions

Density Functional Theory Calculations: A Useful Tool to Investigate Mechanisms of 1,3-Dipolar Cycloaddition Reactions

Spectral Assignment in the [3 + 2] Cycloadditions of Methyl (2E)-3-(Acridin-4-yl)-prop-2-enoate and 4-[(E)-2-Phenylethenyl]acridin with Unstable Nitrile N-Oxides

Application of 2‐Azabicyclo[2.2.1]Hept‐5‐En‐3‐One (Vince Lactam) in Synthetic Organic and Medicinal Chemistry

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