The Versatile Trimethylenemethane Diyl; Diyl Trapping Reactions − Retrospective and New Modes of Reactivity

Allan, Amy Kim; Carroll, Gary L.; Little, R. Daniel

doi:10.1002/(sici)1099-0690(199801)1998:1<1::aid-ejoc1>3.0.co;2-h

Cited by 41 publications

(21 citation statements)

References 52 publications

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“…The 1,3-diradical pathway, on the other hand, has some similarity with the reactivity of 1,3-diradicals of the trimethylenemethane type, generated from bicyclic diazenes, which can be trapped intramolecularly even by a non-activated olefinic CϭC bond. [16] …”

Section: Resultsmentioning

confidence: 99%

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

Kerth

Maas

2001

European J Organic Chem

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Section: Resultsmentioning

confidence: 99%

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

Kerth

Maas

2001

European J Organic Chem

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“…TMM diradicals are a four-electron, three-carbon species and a suitable partner for [3+2] cycloaddition to generate cyclopentane frameworks. [36][37][38][39] These TMM species can be formed from bicyclo [3.1.0]…”

Section: [3+2] Cycloadditionmentioning

confidence: 99%

Strain-Induced Transformations of Bicyclo[3.1.0]hex-1-enes

Ghorai¹,

Lee²

2021

Synthesis

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Bicyclo[3.1.0]hex-1-ene is a highly strained bicyclic intermediate that generates trimethylenemethane (TMM) diradical through breaking the C–C bond of its methylene cyclopropane moiety. The reactivity of bicyclo[3.1.0]hex-1-enes and trimethylenemethane (TMM) diradicals depend on the reaction temperature and substitution patterns. This short review covers various strain-induced transformations of bicyclo[3.1.0]hex-1-enes and their formal [3+2] cycloadditions through TMM diradicals and presents synthetic applications to natural products containing triquinane and tropone structures.1 Introduction2 Early Reports on Bicyclo[3.1.0]hex-1-enes3 Approaches to Form Bicyclo[3.1.0]hex-1-enes4 Structure and Reactivity of Bicyclo[3.1.0]hex-1-enes4.1 Isomerization4.2 Dimerization4.3 [3+2] Cycloaddition4.4 [4+2] Cycloaddition5 Synthetic Applications to Natural Products6 Summary and Outlook

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“…(5) It is possible that the triplet TMM diyl 4T cyclizes to the bridged-fused product P′. 13,14 However, only the linearly-fused product P is observed in the experiment. 11 Why can not the bridged-fused product P′ be obtained?…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigations toward the tandem reactions of N-aziridinyl imine compounds forming triquinanes via trimethylenemethane diyls: mechanisms and stereoselectivity

Qiao

Han

2014

Org. Biomol. Chem.

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In this paper, we have investigated the tandem reaction mechanism for the N-aziridinyl imine compounds forming triquinanes via trimethylenemethane (TMM) diyls in detail. Based on the calculated results, the reaction is initiated by the cleavage of the N-aziridinyl in the substrate, followed by an intramolecular 1,3-dipolar (3 + 2) cycloaddition preferentially leading to a linearly-fused tetrahydrocyclopentapyrazole intermediate. Next, the intermediate loses N2 to form the singlet TMM diyl M3S, which can then undergo another concerted (3 + 2) cycloaddition to generate the linearly-fused cis–trans or cis–syn triquinane products. In addition, M3S can also undergo intersystem crossing to the triplet TMM diyl M3T, and the six possible reaction pathways associated with M3T have also been identified. The calculated results reveal that the cis–trans fused pathway associated with M3S is energetically preferred with the highest free energy barrier of 25.0 kcal mol(−1). In comparison, the cyclization of M3T requires much higher activation free energies (ΔG(≠) = 34.4–57.8 kcal mol(−1)). At the experimental temperature 110 °C, only the linearly-fused cis–trans and cis–syn pathways associated with M3T (ΔG(≠) = 34.4 and 35.5 kcal mol(−1) respectively) are possible. The calculated results also indicate that for both M3S and M3T, the linearly-fused cis–trans triquinane should be the main product, which is consistent with the experimental observation. At last, conformational and NBO analyses on key transition states identified the cis–trans stereocontrol factors. Further calculations indicate that the methyl substituent on the allene group of the reactant substrate improves the stereoselectivity of the reaction but does not affect the rate-determining step.

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The Versatile Trimethylenemethane Diyl; Diyl Trapping Reactions − Retrospective and New Modes of Reactivity

Cited by 41 publications

References 52 publications

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

Strain-Induced Transformations of Bicyclo[3.1.0]hex-1-enes

Theoretical investigations toward the tandem reactions of N-aziridinyl imine compounds forming triquinanes via trimethylenemethane diyls: mechanisms and stereoselectivity

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