Issue 18, 2025

Diazomethyl-λ3-iodane meets aryne: dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes

Abstract

Diazomethyl-λ3-iodanes have recently emerged as carbyne equivalents in organic synthesis, enabling the construction of multi-substituted carbon centers through strategic sequential activation of the diazo and iodane functional groups. Distinct from such reaction modes, we report here on the reactivity of diazomethyl-λ3-iodanes as iodane-bound 1,3-dipoles toward arynes. Equipped with bis(trifluoromethyl)benzyl alcohol-based benziodoxole (BX) moiety, diazomethyl-λ3-iodanes undergo annulation with arynes generated from ortho-silylaryl triflates and cyclic diarylhalonium salts, resulting in indazolyl-λ3-iodanes through [3 + 2] cycloaddition and carbon-to-nitrogen iodane migration. DFT calculations reveal that diazomethyl-BX prefers [3 + 2] cycloaddition with aryne over aryne insertion into the carbon–iodine(III) bond (carboiodanation) and that the subsequent iodane migration proceeds through two consecutive 1,5-iodane shifts. The utility of these indazolyl-BXs as indazole-transfer agents has been demonstrated by α-functionalization of N,N-dimethylaniline derivatives.

Graphical abstract: Diazomethyl-λ3-iodane meets aryne: dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes

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Article information

Article type
Edge Article
Submitted
12 Jan 2025
Accepted
28 Mar 2025
First published
02 Apr 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2025,16, 8053-8059

Diazomethyl-λ3-iodane meets aryne: dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes

S. Otsuki, K. Kanemoto, D. C. Martos, E. Kwon, J. Wencel-Delord and N. Yoshikai, Chem. Sci., 2025, 16, 8053 DOI: 10.1039/D5SC00266D

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