Mild Preparation of Haloarenes by Ipso-Substitution of Arylboronic Acids with N-Halosuccinimides
Christoph Thiebes, G. K. Surya Prakash*, Nicos A. Petasis, George A. Olah
*Loker Hydrocarbon Research Institute and Department of Chemistry,
UniVersity of Southern California, Los Angeles, California 90089-1661, Email:
gprakash
usc.edu
C. Thiebes, G. K. Surya Prakash, N. A. Petasis, G. A. Olah, Synlett, 1998, 141-142.
DOI: 10.1055/s-1998-1614
Abstract
Aryl and heteroaryl boronic acids react with N-iodosuccinimide and N-bromosuccinimide to give the corresponding iodo- and bromo-arenes in good to excellent yields. The reaction is usually highly regioselective and yields only the ipso-substituted product.
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Details
The document discusses a mild method for preparing haloarenes via ipso-substitution of arylboronic acids using N-halosuccinimides. Aryl and heteroaryl boronic acids react with N-iodosuccinimide (NIS) and N-bromosuccinimide (NBS) to yield iodo- and bromoarenes, respectively, in good to excellent yields. The reaction is regioselective, producing only the ipso-substituted products. This method is advantageous over traditional methods as it avoids the use of highly reactive halogens, strong oxidizing agents, or toxic heavy metals. The procedure is particularly useful for synthesizing radiolabeled iodoarenes, which are important in research and medical applications. The reaction typically occurs under mild conditions, with some substrates reacting well at room temperature. However, the method is less effective for preparing chloroarenes and for reactions involving arylboronic esters. The document also acknowledges financial support from various institutions and provides a detailed general procedure for the reaction.
ipso-Nitration of Arylboronic Acids with Chlorotrimethylsilane-Nitrate Salts
G. K. S. Prakash, C. Panja, T. Mathew, V. Surampudi, N. A. Petasi, G. A. Olah, Org. Lett., 2004, 6, 2205-2207.
Key Words
Iodoarenes, N-Iodosuccinimide, Bromoarenes, N-Bromosuccinimide, Arylboronic acids, Ipso-substitution
ID: J60-Y1998-550
