Synthesis of aryl bromides

Name Reactions

Recent Literature

A highly regioselective bromination of activated aromatic compounds has been accomplished using N-bromosuccinimide in tetrabutylammonium bromide. Predominant para-selective monobromination of activated aromatics, rate acceleration for less reactive substrates on addition of acidic montmorillonite K-10 clay, with or without microwave assistance, are the notable features of this protocol.
N. C. Ganguly, P. De. S. Dutta, Synthesis, 2005, 1103-1108.

Highly deactivated aromatic compounds were smoothly monobrominated by treatment with N-bromosuccinimide (NBS) in concentrated sulfuric acid. Mild reaction conditions and simple workup provides a practical and commercially viable route for the synthesis of bromo compounds of deactivated aromatics in good yields.
K. Rajesh, M. Somasundaram, R. Saiganesh, K. K. Balasubramanian, J. Org. Chem., 2007, 72, 5867-5869.

N-Halosuccinimides are efficiently activated in trifluoromethanesulfonic acid and BF₃-H₂O, allowing the halogenations of deactivated aromatics. BF₃-H₂O is more economic, easy to prepare, nonoxidizing, and offers sufficiently high acidity.
G. K. S. Prakash, T. Mathew, D. Hoole, P. M. Esteves, Q. Wang, G. Rasul, G. A. Olah, J. Am. Chem. Soc., 2004, 126, 15570-15776.

A mild palladium-catalyzed, regioselective chlorination, bromination, and iodination of arene C-H bonds using N-halosuccinimides as oxidants is described. These transformations can provide products that are complementary to those obtained via conventional electrophilic aromatic substitution reactions.
D. Kalyani, A. R. Dick, W. Q. Anani, M. S. Sanford, Org. Lett., 2006, 8, 2523-2526.

N,N,N',N'-Tetrabromobenzene-1,3-disulfonylamide (TBBDA) and poly[N-bromobenzene-1,3-disulfonylamide] (PBBS) can be used for the regioselective bromination of aromatic compounds in excellent yields under mild conditions.
R. Ghorbani-Vaghei, H. Jalili, Synthesis, 2005, 1099-1102.

Organotrifluoroborates are rapidly and regioselectively converted into organic bromides in excellent yields under mild conditions, using sodium bromide in the presence of chloramine-T.
G. W. Kabalka, A. R. Mereddy, Organometallics, 2004, 23, 4519-4521.

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.
C. Thiebes, G. K. Surya Prakash, N. A. Petasis, G. A. Olah, Synlett, 1998, 141-142.

ridium-catalyzed borylation of 1,3-disubstituted arenes with B₂pin₂, followed by reaction of the boronic ester with copper(II) bromide or chloride converts arylboronic esters to the corresponding meta-halogenated aryl halides. Various functional groups, such as alkoxy, alkyl, halogen, nitrile, ester, amide, and pivaloyl and TIPS-protected alcohols, are tolerated.
J. M. Murphy, X. Liao, J. F. Hartwig, J. Am. Chem. Soc., 2007, 129, 15434-15435.

Mild, novel procedures have been developed for the syntheses of aryl halides from the corresponding phenols in modest to good yields via boronate ester intermediates.
A. L. S. Thompson, G. W. Kabalka, M. R. Akula, J. W. Huffman, Synthesis, 2005, 547-550.

An efficient version of the Sandmeyer bromination using catalytic amounts of Cu(I)/Cu(II)/phen is highly useful for the preparation of various aryl bromides and dibromides in excellent yields.
I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, P. V. Petrovskii, Synthesis, 2007, 2534-2538.

A standard ortho-lithiation/bromination procedure applied to bromoarenes resulted in poor yields of the corresponding 1,2-dibromoarenes. Transmetalation of the aryllithium intermediates with ZnCl₂, followed by bromination, improved the yields of the synthetically useful 1,2-dibromoarenes dramatically.
K. Menzel, E. L. Fisher, L. DiMichele, D. E. Frantz, T. D. Nelson, M. H. Kress, J. Org. Chem., 2006, 71, 2188-2191.

Use of a solvent with greater density than the fluorous phase is an alternative to the U-tube method in phase-vanishing reactions in cases where both reactants are less dense than the fluorous phase.
N. K. Jana, J. G. Verkade, Org. Lett., 2003, 5, 3787-3790.