Halo-Jacobsen Rearrangement Induced by Steric Repulsion between <i>peri</i>-Iodo Groups

Iwai, Kento; Nishiguchi, Noa; Nishiwaki, Nagatoshi

doi:10.1021/acs.joc.3c00165

Cited by 3 publications

(1 citation statement)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More recently, we also reported the transformation of 1,8-diiodonaphthalene via non-electronical activation. The 1,8-diiodonaphthalene showed various reactivities to undergo a homocoupling reaction, leading to binaphthyl and the rearrangement of the iodo group ( Scheme 1 c) [ 6 ].…”

Section: Introductionmentioning

confidence: 99%

A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring

2023

Self Cite

View full text Add to dashboard Cite

A systematic study on the distortion of a naphthalene ring was performed using steric repulsion between peri-substituents at the 1- and 8-positions. The introduction of bromo groups into the methyl groups of the 1,8-dimethylnaphthalene enhanced the steric repulsion to distort the naphthalene ring. X-ray crystallography revealed that 1,8-bis(bromomethyl)naphthalene had a vertical distortion with a 11.0° dihedral angle (α) between peri-substituents which disturbed the coplanarity of the naphthalene ring. On the other hand, the dihedral angle of 1,8-bis(dibromomethyl)naphthalene was smaller (α = 8.3°) despite the bulkier substituents. In this case, horizontal distortion of the naphthalene ring increased. These distortions should non-electronically activate the naphthalene framework. In order to evaluate their reactivity, nitration and hydrogenation were carried out; however, the 1,8-bis(dibromomethyl)naphthalene was intact under the employed conditions. A DFT calculation suggested that the inertness of the 1,8-bis(dibromomethyl)naphthalene is presumably due to the negative hyperconjugation of the (dibromo)methyl group.

show abstract

Section: Introductionmentioning

confidence: 99%

A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring

2023

Self Cite

View full text Add to dashboard Cite

show abstract

Non‐Electronic Activation of Anthracenes Using Steric Repulsion of the 9‐Substituent with Chloro Groups at the peri‐Positions

Indah Reza,

Iwai,

Nishiwaki

2024

Asian J Org Chem

View full text Add to dashboard Cite

We investigated how the introduction of substituent at the 9‐ or 10‐position of the 1,8‐dichloroanthracene framework affects the horizontal and vertical distortions of the anthracene rings. The 9‐substituted anthracenes showed higher distortions than their 10‐substituted counterparts due to the steric repulsion with two chloro groups at the peri‐positions. The distortion of anthracene framework affected their reactivity. Indeed, 9‐substituted anthracenes exhibited higher reactivity to undergo the Diels–Alder reaction with maleic anhydride, which was a result of non‐electronic activation.

show abstract

Unsymmetrization of 1,8-Dibromonaphthalenes by Acid-Induced Halogen Dance Reaction

Iwai,

Nishiwaki

2024

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

A simple and powerful tool for preparing uncommon bromoarenes via the unsymmetrization of a naphthalene ring was developed. The steric repulsion between the peri-bromo groups of 1,8-dibromonaphthalene distorts the naphthalene ring, allowing for nonelectronical activation. Ring distortion facilitates the 1,2-rearrangement of the bromo group, affording 1,7-dibromonaphthalene upon treatment with trifluoromethanesulfonic acid (halogen dance reaction). For 1,4,5,8-tetrabromonaphthalene, stepwise 1,2-rearrangements proceeded successively to furnish 1,3,5,7-tetrabromonaphthalene. Density functional theory calculations suggest that this reaction is initiated by ipso-protonation, with a subsequent 1,2-rearrangement occurring via the bromonium transition state. Utilizing 1,7-dibromonaphthalene, which is characterized by two C−Br bonds arranged at a 60°angle, a unique metal−organic framework comprising a 52-membered ring network was synthesized.

show abstract

Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups

Cited by 3 publications

References 23 publications

A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring

A Study of the Correlation between the Bulkiness of peri-Substituents and the Distortion of a Naphthalene Ring

Non‐Electronic Activation of Anthracenes Using Steric Repulsion of the 9‐Substituent with Chloro Groups at the peri‐Positions

Unsymmetrization of 1,8-Dibromonaphthalenes by Acid-Induced Halogen Dance Reaction

Contact Info

Product

Resources

About