Categories: C-Br Bond Formation >
Synthesis of aryl bromides
Name Reactions
Recent Literature
The Lewis base Trip-SMe (Trip = triptycenyl) catalyzes an electrophilic
halogenation of unactivated aromatic compounds using N-halosuccinimides (NXS) at
ambient temperature in the presence of AgSBF6 as source of a
non-coordinating anion. The π system of the triptycenyl functionality exerts a
crucial role for the enhancement of electrophilicity.
Y. Nishii, M. Ikeda, Y. Hayashi, S. Kawauchi, M. Miura, J. Am. Chem. Soc.,
2020, 142, 1621-1629.
DMSO as a mild and inexpensive oxidant enables an efficient and practical
bromination and iodination of arenes with HX (X = Br, I) reagents. This
oxidative system is amenable to late-stage bromination of natural products and
kilogram-scale conversions.
S. Song, X. Sun, X. Li, Y. Yuan, N. Jiao, Org. Lett.,
2015,
17, 2886-2889.
The use of a hexafluoroisopropanol as solvent enables a mild and regioselective
halogenation of a broad range of arenes and heterocycles with N-halosuccinimides
in good yields. In addition, the versatility of the method is demonstrated by
the development of one-pot sequential dihalogenation and halogenation-Suzuki
cross-coupling reactions.
R.-J. Tang, T. Milcent, B. Crousse, J. Org. Chem.,
2018, 83, 930-938.
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.
Moderately deactivated arenes are efficiently brominated with 0.34 eq.
tribromoisocyanuric acid in trifluoroacetic acid at room
temperature. The use of trifluoroacetic acid avoids the polybromination of
the substrate, as can be observed in the same reaction performed in 98% H2SO4.
L. S. de Almeida, M. C. S. de Mattos, P. M. Esteves, Synlett, 2013, 24,
603-606.
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, 15770-15776.
Vanadium pentoxide very effectively promotes the bromination of organic
substrates, including selective bromination of some aromatics, by
tetrabutylammonium bromide in the presence of hydrogen peroxide. The reaction
offers mild conditions, high selectivity, yield, and reaction rate, and
redundancy of bromine and hydrobromic acid.
U. Bora, G. Bose, M. K. Chaudhuri, S. S. Dhar, R. Gopinath, A. T. Khan, B. K.
Patel,
Org. Lett., 2000, 2, 247-249.
A highly para-selective halogenation of arenes bearing electron-donating
coordinating groups in the presence of a dimidazolium salt rpovides p-haloarenes
in good yields. A plausible mechanism for the catalytic reaction is proposed.
J. Chen, X. Xiong, Z. Chen, J. Huang,
Synlett, 2015, 26, 2831-2834.
A highly efficient, rapid and regioselective protocol for the ring bromination
of aromatic compounds under mild conditions can be conducted with ammonium
bromide as a source of bromine source and Oxone as an oxidant. Various aromatic
compounds reacted smoothly to give the corresponding monobrominated products in
good yields in very short reaction times.
N. Naresh, M. A. Kumar, M. M. Reddy, P. Swamy, J. B. Nanubolu, N. Narender, Synthesis, 2013, 45,
1497-1504.
A simple, efficient and mild method for the selective bromination of
activated aromatic compounds using ammonium bromide as the source of bromine and
Oxone as the oxidant in methanol or water as solvent proceeds at ambient temperature in good yields without a catalyst.
M. A. Kumar, C. N. Rohitha, S. J. Kulkarni, N. Narender, Synthesis, 2010,
1629-1632.
Iodobenzene can be used as a recyclable catalyst in combination with m-chloroperbenzoic
acid as the terminal oxidant for an efficient and regioselective monobromination
of electron-rich aromatic compounds. The bromination of electron-rich aromatic
compounds with lithium bromide was fast in tetrahydrofuran at room temperature,
providing regioselective monobrominated products in good yields.
Z. Zhou, X. He, Synthesis, 2011,
207-209.
AuCl3-catalyzed halogenations of aryl borononates with N-halosuccinimides
enables a convenient synthesis of aromatic boronates bearing halogen
substituents in the aromatic ring.
D. Qiu, F. Mo, Z. Zheng, Y. Zhang, J. Wang, Org. Lett., 2010,
12, 5474-5477.
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.
Aryl triflates were simply transformed to aryl bromides or iodides in the
presence of LiBr or NaI and [Cp*Ru(MeCN)3]OTf as catalyst. A similar
transformation of alkenyl sulfonates and phosphates can be conducted under mild
conditions to provide the corresponding halides.
Y. Imazaki, E. Shirakawa, R. Ueno, T. Hayashi, J. Am. Chem. Soc., 2012,
134, 14760-14761.
A facile Pd-catalyzed conversion of aryl and vinyl triflates allows convenient
access to various aryl, heteroaryl, and vinyl halides in good to excellent
yields and with greatly simplified conditions relative to our previous report.
J. Pan, X. Wang, Y. Zhang, S. L. Buchwald, Org. Lett., 2011,
13, 4974-4976.
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.
Halogen abstraction from bromotrichloromethane and diiodomethane enables a
metal-free synthesis of aryl bromides and iodides from anilines without
isolation of diazonium salts. The transformation offers short reaction times, a
simple workup, and insensitivity to moisture and air and avoids excess
halogenation. This method represents a convenient alternative to the classic
Sandmeyer reaction.
D. A. Leas, Y. Dong, J. L. Vennerstrom, D. E. Stack, Org. Lett.,
2017, 19, 2518-2521.
Using cyano as the directing group, a palladium-catalyzed ortho-halogenation
(I, Br, Cl) reaction gave good to excellent yields. The method is compatible to
arylnitriles with either electron-withdrawing or electron-donating groups. The
present method was successfully applied to the synthesis of the precursors of
paucifloral F and isopaucifloral F.
B. Du, X. Jiang, P. Sun, J. Org. Chem., 2013,
78, 2786-2791.
A high-yielding, general, and practical ortho bromination and iodination
reaction of different classes of aromatic compounds occurs by Rh(III)-catalyzed
C-H bond activation methodology.
N. Schröder, J. Wencel-Delord, F. Glorius, J. Am. Chem. Soc., 2012,
134, 8298-8301.
Silver carbonate or nickel(II) chloride catalyzes an ortho-C-H bond halogenation of anilides and
N-aryl carbamates with N-halosuccinimides to provide 2-haloanilides and carbamates, which may serve as starting
materials for the synthesis of pharmaceutically and biologically active
compounds.
E. Kianmehr, H. Afaridoun, Synthesis, 2021, 53,
1513-1523.
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.
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
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.