Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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.
See this image and copyright information in PMC

References

    1. Yoshimura A. Zhdankin V. V. Chem. Rev. 2016;116:3328–3435. doi: 10.1021/acs.chemrev.5b00547. - DOI - PubMed
    2. Hari D. P. Caramenti P. Waser J. Acc. Chem. Res. 2018;51:3212–3225. doi: 10.1021/acs.accounts.8b00468. - DOI - PubMed
    3. Charpentier J. Fruh N. Togni A. Chem. Rev. 2015;115:650–682. doi: 10.1021/cr500223h. - DOI - PubMed
    4. Yoshimura A. Zhdankin V. V. Chem. Rev. 2024;124:11108–11186. doi: 10.1021/acs.chemrev.4c00303. - DOI - PMC - PubMed
    1. Wang Z. Herraiz A. G. del Hoyo A. M. Suero M. G. Nature. 2018;554:86–91. doi: 10.1038/nature25185. - DOI - PubMed
    1. Taylor M. T. Nelson J. E. Suero M. G. Gaunt M. J. Nature. 2018;562:563–568. - PMC - PubMed

    1. For reviews, see:

    2. Zhang C. Wan J.-P. Chem. - Eur. J. 2024;30:e202302718. - PubMed
    3. Timmann S. Alcarazo M. Chem. Commun. 2023;59:8032–8042. - PMC - PubMed
    1. He Q. Zhang Q. Rolka A. B. Suero M. G. J. Am. Chem. Soc. 2024;146:12294–12299. - PMC - PubMed
    2. Wu F.-P. Chintawar C. C. Lalisse R. Mukherjee P. Dutta S. Tyler J. Daniliuc C. G. Gutierrez O. Glorius F. Nat. Catal. 2024;7:242–251. doi: 10.1038/s41929-023-01089-x. - DOI - PMC - PubMed

LinkOut - more resources