N-Chlorosuccinimide (NCS) is a chlorinating and oxidizing agent that is used as source for chlorine in radical reactions and various electrophilic additions.
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, efficient, Cu(I)-catalyzed method for the synthesis of aryl chlorides from arylboronic acids is particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient in the absence of Cu catalysis.
H. Wu, J. Hynes, Jr., Org. Lett., 2010, 12, 1192-1195.
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.
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 intramolecular chloroamination of allenes with N-chlorosuccinimide proceeds under mild conditions in the presence of a 1,10-phenanthroline-ligated cationic silver complex and 2,6-lutidine as a base. The reaction tolerates various functional groups. The chloroamination products are useful synthetic intermediates and can be easily transformed into functionalized 3-pyrroline and pyrrole derivatives.
M. Sai, S. Matsubara, Org. Lett., 2011, 13, 4676-4679.
Various 2-aryl-3-arylamino-2-alkenenitriles give N-arylindole-3-carbonitriles in a one-pot manner through NBS- or NCS-mediated halogenation followed by Zn(OAc)2-catalyzed intramolecular cyclization. The process involves the formation of arylnitrenium ion intermediates, which undergo an electrophilic aromatic substitution to give the cyclized N-arylindoles.
Q. Yan, J. Luo, D. Zhang-Negrerie, H. Li, X. Qi, K. Zhao, J. Org. Chem., 2011, 76, 8690-8697.
A divergent and regioselective synthesis of either 3-substituted benzisoxazoles or 2-substituted benzoxazoles from readily accessible ortho-hydroxyaryl N-H ketimines proceeds in two distinct pathways through a common N-Cl imine intermediate: (a) N-O bond formation to form benzisoxazole under anhydrous conditions and (b) NaOCl mediated Beckmann-type rearrangement to form benzoxazole, respectively.
C.-y Chen, T. Andreani, H. Li, Org. Lett., 2011, 13, 6300-6303.
A fluorous (S)-pyrrolidine-thiourea bifunctional organocatalyst shows good activity and enantioselectivity for direct α-chlorination of aldehydes using N-chlorosuccinimide (NCS) as the chlorine source. The catalyst can be recovered from the reaction mixture by fluorous solid-phase extraction with excellent purity for direct reuse.
L. Wang, C. Cai, D. P. Curran, W. Zhang, Synlett, 2010, 433-436.
A direct organocatalytic enantioselective α-chlorination of aldehydes proceeds for a series of different aldehydes with NCS as the chlorine source using easily available catalysts such as L-proline amide and (2R,5R)-diphenylpyrrolidine. The α-chloro aldehydes are obtained in very good yield and high enantioselectivity.
N. Halland, A. Braunton, S. Bachmann, M. Marigo, K. A. Jorgensen, J. Am. Chem. Soc., 2004, 126, 4790-4791.
A smooth oxidation of several thiol derivatives by a combination of N-chlorosuccinimide and dilute hydrochloric acid afforded the corresponding sulfonyl chlorides in good yield.
A. Nishiguchi, K. Maeda, S. Miki, Synthesis, 2006, 4131-4134.
In situ preparation of sulfonyl chlorides from thiols by oxidation with N-chlorosuccinimide (NCS), tetrabutylammonium chloride, and water followed by reaction with amine or sodium azide in the same reaction vessel enables a convenient synthesis of sulfonamides and sulfonyl azides.
H. Veisi, R. Ghorbani-Vaghei, S. Hemmati, J. Mahmoodi, Synlett, 2011, 2315-2320.