N-Iodosuccinimide (NIS)
N-Iodosuccinimide (NIS) is an iodinating agent that is used for various electrophilic iodinations and as source for iodine in radical reactions.
Recent Literature
Various methoxy- or methyl-substituted aromatic compounds were regioselectively
iodinated with N-iodosuccinimide and and a catalytic amount of
trifluoroacetic acid with excellent yields under mild conditions and short
reaction times.
A.-S. Castanet, F. Colobert, P.-E. Broutin, Tetrahedron Lett., 2002,
43, 5047-5048.
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.
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.
Reliable, operationally simple, catalytic α-selective
hydroalumination reactions proceed in the presence of diisobutylaluminum
hydride and (Ni(dppp)Cl2), and, unlike
uncatalyzed transformations, generate little or no alkynylaluminum
byproducts. The derived α-vinyl halides and boronates can be synthesized
through direct treatment with the appropriate electrophiles.
F. Gao, A. H. Hoveyda, J. Am. Chem. Soc., 2010,
132, 10961-10963.
Using triethylamine as catalyst in Hunsdiecker reactions with N-halosuccinimides
as Br+ or I+ source, cinnamic acids, and propiolic acids are
converted to the corresponding α-halostyrenes and 1-halo-1-alkynes in good isolated yields within 1-5 min.
J. Prakash, S. Roy, J. Org. Chem.,
2002, 67, 7861-7864.
An efficient protocol for a highly stereoselective one-pot synthesis of (E)-β-aryl
vinyl iodides and (E)-β-aryl vinyl bromides from styrenes is based on a
ruthenium-catalyzed silylative coupling followed by a N-halosuccinimide-mediated
halodesilylation reaction.
P. Pawluć, G. Hreczycho, J. Szudkowska, M. Kubicki, B. Marciniec, Org. Lett., 2009,
11, 3390-3393.
A direct asymmetric iodination reaction of aldehydes with NIS catalyzed by a
novel axially chiral bifunctional amino alcohol represents a rare example of a
highly enantioselective synthesis of optically active α-iodoaldehydes.
T. Kano, M. Ueda, K. Maruoka, J. Am. Chem. Soc., 2008,
130, 3728-3729.
The reaction of alkynes with N-iodosuccinimides and water at 70˚C allows
a convenient and practical approach to α-diketones.
M. Niu, H. Fu, Y. Jiang, Y. Zhao, Synthesis, 2008,
2879-2882.
An efficient synthesis of α-iodo/bromo-α,β-unsaturated aldehydes/ketones
directly from propargylic alcohols is catalyzed collaboratively by Ph3PAuNTf2
and MoO2(acac)2, and Ph3PO as an additive helps
suppress undesired enone/enal formation. Notable features of this method include
low catalyst loadings, mild reaction conditions, and mostly good
diastereoselectivity.
L. Ye, L. Zhang, Org. Lett., 2009,
11, 3646-3649.
A catalytic amount of Au(PPh3)NTf2 converts readily
accessible propargylic acetates into versatile linear α-iodoenones in good to
excellent yields. Very good Z-selectivities are observed for aliphatic
propargylic acetates.
M. Yu, G. Zhang, L. Zhang, Org. Lett., 2007,
9, 2087-2090.
A new silver-catalyzed highly regio- and stereoselective difunctionalization
reaction of simple terminal alkynes gives (Z)-β-haloenol acetate
derivatives in good yields. The resulting products are versatile intermediates
in organic synthesis.
Z. Chen, J. Li, H. Jiang, S. Zhu, Y. Li, C. Qi, Org. Lett., 2010,
12, 3262-3265.
A sequence consisting of an electrophilic cyclization in the presence of N-iodosuccinimide
(NIS) and an 1,2-migration allows the construction of 4-iodo-3-furanones from
2-alkynyl-2-silyloxy carbonyl compounds. In a more versatile variant, AuCl3
catalyzes the tandem reaction in the presence of NIS to provide highly
substituted heterocycles in good yields.
B. Crone, S. F. Kirsch, J. Org. Chem., 2007,
72, 5435-5438.
Various tert-butyldimethylsilyl ethers are easily removed in excellent
yields by treatment with a catalytic amount of N-iodosuccinimide in
methanol. This method allows a selective deprotection of TBDMS ethers of
alcohols in the presence of TBDMS ethers of phenols.
B. Karimi, A. Zamani, D. Zarayee, Tetrahedron Lett., 2004,
45, 9139-9141.
Use of La(OTf)3 as a Lewis acid promoter for N-iodosuccinimide-mediated
activation of thioglycosides enables a smooth glycosylation reaction with good
to excellent yields and stereoselectivity.
S. Mukherjee, B. Mukhopadhyay, Synlett, 2010,
2853-2856.
Gold(I)-catalyzed cycloisomerization of 1-(2-(tosylamino)phenyl)prop-2-yn-1-ols
enables the preparation of 1H-indole-2-carbaldehydes and (E)-2-(iodomethylene)indolin-3-ols
in the presence of N-iodosuccinimide (NIS). The reactions were shown to
be operationally simplistic and proceed efficiently for a wide variety of
substrates, affording the corresponding products in very good yields.
P. Kothandaraman, S. R. Mothe, S. S. M. Toh, P. W. H. Chan, J. Org. Chem., 2011,
76, 7633-7640.
The intramolecular cyclization of 1-azido-2-(2-propynyl)benzene proceeds
smoothly in the presence of electrophilic reagents in CH3NO2
at room temperature or in the presence of catalytic amounts of AuCl3/AgNTf2
in THF at 100°C to afford the corresponding quinolines 2 in good to high yields.
Z. Huo, I. D. Gridnev, Y. Yamamoto, J. Org. Chem., 2010,
75, 1266-1270.
