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. 2025 Apr 2;16(18):8053-8059.
doi: 10.1039/d5sc00266d. eCollection 2025 May 7.

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

Shinya Otsuki  1 , Kazuya Kanemoto  1 , Daniel Carter Martos  2 , Eunsang Kwon  3   4 , Joanna Wencel-Delord  2   5 , Naohiko Yoshikai  1
Affiliations

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

Shinya Otsuki et al. Chem Sci. .

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.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Background and summary of the present study.
Fig. 1
Fig. 1. Computed energy profile for the reaction between diazomethyl-BX and benzyne (level: M06-2X/6-311++G(2df,2p)-SDD(for I)/SMD(THF)//M06-2X/6-31G(d)-SDD(for I)). Bond lengths are indicated in Å.
Scheme 2
Scheme 2. Use of indazolyl-BXs as group transfer agents for the functionalization of N,N-dimethylaniline derivatives.
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