The Rearrangement of the Neophyl Radical

Seubold, Frank H.

doi:10.1021/ja01106a535

Cited by 36 publications

(9 citation statements)

References 3 publications

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“…The nmr spectrum of the mixture of 3-methyl-5-methylthioeyclopentenes shows it to be a 70:30 mixture of the trans and cis isomers. The spectrum exhibits a total integration equivalent to 11 protons with the region for the two methyl doublets (r 8.92 and 8.97) integrating for an area of two protons. The other protons appeared as in the undeuterated compounds.…”

Section: Methodsmentioning

confidence: 99%

Reactive intermediates in the bicyclo[3.1.0]hexyl and bicyclo[3.1.0]hexylidene systems. VI. Free-radical addition of methanethiol and methanethiol-d to bicyclo[3.1.0]hex-2-ene

Freeman¹,

Grostic²,

Raymond³

1971

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

Reactive intermediates in the bicyclo[3.1.0]hexyl and bicyclo[3.1.0]hexylidene systems. VI. Free-radical addition of methanethiol and methanethiol-d to bicyclo[3.1.0]hex-2-ene

Freeman¹,

Grostic²,

Raymond³

1971

J. Org. Chem.

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“…This effect was experimentally confirmed by a competition experiment involving a 1:1 mixture of 1a/1b (excess), n-BuLi and EtO2CCH2I that gave 4aa/4ba as 1:1.5 mixture (see supporting information). [36] [37] [38][39] leading to a boryl radical-anion D which could then propagate the chain via a reductive SET. Indeed, boryl radical anions such as BH3 •and BH2CN •are known to abstract efficiently iodine atom presumably via a SET process.…”

Section: Scheme 2 Discovery Of Reactionmentioning

confidence: 99%

Radical‐Triggered Three‐Component Coupling Reaction of Alkenylboronates, α‐Halocarbonyl Compounds, and Organolithium Reagents: The Inverse Ylid Mechanism

Tappin

Gnägi‐Lux

Renaud

2018

Chemistry A European J

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An operationally simple protocol to affect a radical addition to alkenylboronates that spontaneously undergo a [1,2]-metalate shift is described. Overall, the reaction is a three-component coupling of an organolithium, alkenylboronic ester, and halide which takes place with broad scope and good to excellent yields. Experimental mechanistic investigations support the formation of a boron inverse ylid intermediate.

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“…The high reactivity of the related monoradicals is well known experimentally. [29] In sharp contrast, ring-opening of the unsubstituted cyclopropane needs a comparatively high energy. According to experimental heats of formation, the dissociation energy amounts to 50 kcal mol Ϫ1 .…”

Section: Energetics Of the Parent Reactionmentioning

confidence: 99%

“…According to experimental heats of formation, the dissociation energy amounts to 50 kcal mol Ϫ1 . [29] For that reason the regioisomeric spiro[cyclopropane-1,4Ј-isoxazolidines] 12 with isolated three-membered rings are not reactive.…”

Section: Energetics Of the Parent Reactionmentioning

confidence: 99%

A Combined Density Functional and ab initio Quantum Chemical Study of the Brandi Reaction

Ochoa¹,

Mann²,

Sperling³

et al. 2001

Eur. J. Org. Chem.

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The Brandi reaction is the transformation of spiro[cyclopropane-1,5Ј-isoxazolidines] into tetrahydropyridones under thermal conditions. According to calculations performed by the restricted and unrestricted density functional theory and post-Hartree−Fock single-and multireference methods of ab initio quantum chemistry, the reaction proceeds through two biradical intermediates. These intermediates result from the homolytic cleavage of the N−O bond of the isoxazolidine ring in the first step, and the homolytic cleavage of one of the C−C bonds of the spiro-fused cyclopropane in the second. The activation energy of the rate-determining first step of the parent reaction amounts to about 40 kcal mol −1 at the RDFT/ UDFT level of theory. This energy is not much higher than

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The Rearrangement of the Neophyl Radical

Cited by 36 publications

References 3 publications

Reactive intermediates in the bicyclo[3.1.0]hexyl and bicyclo[3.1.0]hexylidene systems. VI. Free-radical addition of methanethiol and methanethiol-d to bicyclo[3.1.0]hex-2-ene

Reactive intermediates in the bicyclo[3.1.0]hexyl and bicyclo[3.1.0]hexylidene systems. VI. Free-radical addition of methanethiol and methanethiol-d to bicyclo[3.1.0]hex-2-ene

Radical‐Triggered Three‐Component Coupling Reaction of Alkenylboronates, α‐Halocarbonyl Compounds, and Organolithium Reagents: The Inverse Ylid Mechanism

A Combined Density Functional and ab initio Quantum Chemical Study of the Brandi Reaction

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