Recent Developments in Arylation of N-Nucleophiles via Chan-Lam Reaction: Updates from 2012 Onwards

Abstract

: ''Chan-Evans-Lam'' (CEL) reaction is the copper-mediated cross-coupling of N-nucleophiles with boronic acids that was independently reported in 1998 by Chan, Evans, and Lam for the first time. This reaction is accomplished at room temperature with a remarkably wide range of nucleophiles. In the recent decade, it has been particularly attractive as a convenient method for constructing the various C–N bonds in organic synthesis. Therefore, a comprehensive survey through all reported process was crucial. In this review, we summarized research progress about N-Arylation, based on the type of N-nucleophile involved in this reaction and catalysts from 2012 onwards.

N,N′-Dimethylurea as an efficient ligand for the synthesis of pharma-relevant motifs through Chan–Lam cross-coupling strategy

“…), solvent ( 5 Organic & Biomolecular Chemistry Paper different polar solvents like methanol (MeOH), isopropanol (IP), and ethanol (EtOH) and also without adding DMU. But, better results were not obtained (Table 1, entries [13][14][15][16].…”

“…The amount of the base was fixed at 2 equivalents for all the optimization studies as no conversion was obtained with 1 equivalent of the base (Table 6, entries 1-5). It was seen that except for K 2 CO 3 , inorganic bases like K 3 PO 4 and NaO t Bu gave only slightly higher yields of the corresponding secondary amides (Table 6, entries [13][14][15]. On the other hand, organic bases like DBU, DIPEA, Et 3 N, DABCO and DMAP provided improved yields of the product and the highest yield was obtained with Et 3 N (Table 6, entries [16][17][18][19][20].…”

“…The domain of carbon-nitrogen bond formation is predominantly occupied by three strategies: the Ullmann-Goldberg reaction, [1][2][3] the Buchwald-Hartwig reaction, [4][5][6][7] and the Chan-Lam cross-coupling reaction. [8][9][10][11][12][13] Of these, the adopted approach depends on the starting materials, the choice of metal and the type of C-N transformation desired. With a universal demand for more than 100 years, C-N bond formations continue to enthrall synthetic chemists due to their notable biological activities.…”

Synthesis of Open‐Cage Fullerene Derivatives Containing Multiple Hydroxyl and Amino Groups on the Rim of the Orifice†

“…The amino groups on the two phenyl groups in 3b are similar to those in other aniline derivatives. For example, treating 3b with phenyl boric acid resulted in compound 6 , analogous to the Chan‐Evans‐Lam coupling reaction [ 20 ] (Scheme 2). But the yield was less than 10%.…”

Utilization of Aryl(TMP)iodonium Salts for Copper-Catalyzed N-Arylation of Isatoic Anhydrides: An Avenue to Fenamic Acid Derivatives and N,N′-Diarylindazol-3-ones

“…Formulation of a practical strategy for arylation of heterocyclic molecules or heteroatom-based nucleophiles is of paramount importance and a powerful tool to architect the key building blocks in organic synthesis and medicinal chemistry . In the realm of arylation chemistry, the hypervalent iodine arylating compound i.e., diaryl-λ 3 -iodanes, (well known as diaryliodonium salts) have witnessed a dramatic upsurge as an efficient and versatile aryl-transferring reagent, either in metal-free or transition-metal-catalyzed methods . Though the inherent electrophilicity of this aryl donor is immensely applauded in metal-free arylation protocols, the arylation methodologies of diaryliodonium salts under copper catalysis are also quite familiar and illustrate remarkable examples of arylation reactions .…”