Phenyldiimine in the Reduction of Diazonium Salts by Sodium Tetrahydridoborate

König, Eckehard; Musso, Hans; Záhorszky, U. I.

doi:10.1002/anie.197200452

Cited by 3 publications

(1 citation statement)

References 10 publications

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“…On the other hand, in methanol both the C–H (96.0 ± 0.1 kcal mol –1 ) and O–H (104.2 ± 0.9 kcal mol –1 ) bonds were cleaved with a ratio of ca. 9:1 . Analogously, in ethanol and t BuOH, a competitive hydrogen transfer from O–H and C–H bonds occurred, depending on both statistics and thermodynamic effects.…”

Section: Discussionmentioning

confidence: 93%

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

et al. 2017

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The reactivity of α,n-didehydrotoluenes (DHTs) in protic media (organic/aqueous mixtures) was explored by means of a combined computational and experimental approach. These intermediates were generated via a photoinduced double elimination process occurring in (chlorobenzyl)trimethylsilanes and led to the formation of a varied products distribution, depending on the isomer tested. Irradiation of ortho- and para-derivatives resulted, respectively, in the formation of triplet α,2- and α,4-DHTs, whose diradical reactivity led to both radical and polar products. On the other hand, irradiation of the meta-precursor led to the singlet α,3-DHT isomer. The latter showed a marked preference for the formation of polar products and this was rationalized, as supported by computational evidence, via the involvement of a zwitterionic species arising through interaction of the nucleophilic solvent with the benzylic position of the DHT.

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Section: Discussionmentioning

confidence: 93%

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

et al. 2017

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Nucleophilic Addition to Singlet Diradicals: Heterosymmetric Diradicals

Wenthold

Winter

2018

J. Org. Chem.

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In the preceding paper, we examined the addition of nucleophiles to homosymmetric diradicals and showed that the reaction occurs with no symmetry restrictions or other electronic impediments. In this work, we examine the addition of nucleophiles to heterosymmetric diradicals, by using the addition of chloride to m-dehydrotoluene as a case study. Using CASPT2 and density functional theory calculations, we show that the addition of chloride to m-dehydrotoluene is predicted to be barrierless at the asymptotic limit if C symmetry is broken, and the reaction is allowed to proceed through a nonplanar geometry. A nonplanar cyclic allene acts as the transitioning structure between open-shell and closed-shell species for the addition of chloride, with a continuous and smooth changing of the wave function by the evolution of orbital and configuration interaction coefficients, such that there is no abrupt switch from diradical to closed-shell species along the reaction coordinate. The overall conclusion from our analysis is that both homosymmetric and heterosymmetric diradicals can undergo reaction with closed-shell reagents without a barrier, and one cannot rule out the direct addition of nucleophiles to diradicals when considering the reaction mechanism.

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Radical-chain, electron-transfer dehalogenation reactions

Bunnett¹

1992

Acc. Chem. Res.

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My chief motivation in writing this Account is to tell about studies in my laboratory of the radical-induced dehalogenation of aryl halides by alkoxide ions. But also I want to point out that the reaction we have studied is of a broad category not well recognized, and to call attention to other processes within that category.Most of the reactions in the category of interest conform to the abstract notation of eq 1. A few reactions appear to conform to eq 2. The category is RX + ZH" -RH + Z + X-(1) RX + ZH -RH + Z+ + X"(2) characterized by its mechanism, prominent features of which are abstraction of a hydrogen atom from ZH" or ZH, respectively, by radical R', to form Z*" or Z', which are good electron donors, and ensuing transfer of an electron to RX, forming RX'", which fragments to regenerate R*.

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Phenyldiimine in the Reduction of Diazonium Salts by Sodium Tetrahydridoborate

Cited by 3 publications

References 10 publications

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

Nucleophilic Addition to Singlet Diradicals: Heterosymmetric Diradicals

Radical-chain, electron-transfer dehalogenation reactions

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