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Updated: Jul 28, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups
Kento Iwai1,2, Noa Nishiguchi1, Nagatoshi Nishiwaki1,2
1School of Environmental Science and Engineering, Kochi University of Technology, Kami, Kochi 782-8502, Japan.
Abstract:
The naphthalene ring is distorted due to steric repulsion between iodo groups at the peri-positions. Due to the distortion, 1,8-diiodonaphthalene underwent a halo-Jacobsen rearrangement when treated with trifluoromethanesulfonic acid, producing 1,5-diiodonaphthalene and 1,4-diiodonaphthalene. In this reaction, acid-induced dehalogenative homocoupling also proceeded to form 4,4'-diiodo-1,1'-binaphthyl. The reaction selectivity could be controlled by varying the reaction temperature. DFT calculations and some control experiments revealed that these compounds were formed by different pathways.
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