Copper-Catalyzed Direct Arylation of Cyclic Enamides Using Diaryliodonium Salts

Abstract

A convenient method for the copper(II)-catalyzed direct arylation of cyclic and nonaromatic enamides using diaryliodonium salts has been developed. The reaction demonstrates large functional group tolerance, good yields, and total regioselectivity with a C(3)-functionalization. The synthetic potential of this coupling was explored by using a range of readily accessible diaryliodonium salts and enamides.

Progresses of Diaryliodonium Salts in Organic Reactions

“…Greaney 等 [34] 报道了 Herrmann-Beller 钯催化剂催化 的二芳基碘鎓盐与非活化芳烃的 C-H 芳基化反应(Eq. 2013 年, Gillaizeau 等 [36] 报道了以烯胺 35 为底物, Cu(OTf) 2 催化与二芳基碘鎓盐的偶联反应, 得到 3-位芳 基化烯胺产物 36 (Eq. 5).…”

Direct Metal‐Catalyzed Regioselective Functionalization of Enamides

“…Gillaizeau and co-workers also developed a copper-catalyzed direct arylation of cyclic enamides using diaryliodonium salts (Scheme 42). [55] The reaction demonstrated large functional group tolerance, good yields, and total regioselectivity with a C3-functionalization. Mechanistically a pre-formed Cu III -aryl species underwent electrophilic addition at the electron-rich C3-position of the enamide.…”

Ruthenium(II)‐Catalyzed Chelation‐Assisted Arylation of CH Bonds with Diaryliodonium Salts

“…[6] Since the time when these studies appeared in the literature, the catalytic arylation of C À H bonds with diaryliododium salts has attracted considerable attention (Scheme 1). [7][8][9][10] The most extensively used catalysts in the transformation of C À H bonds with diaryliododium salts are palladium and copper complexes. [7,8] However, it is well known that other transition-metal complexes, such as those of ruthenium, rhodium, iridium, and nickel are also highly active catalysts in the catalytic functionalization of CÀH bonds.…”

“…[7][8][9][10] The most extensively used catalysts in the transformation of C À H bonds with diaryliododium salts are palladium and copper complexes. [7,8] However, it is well known that other transition-metal complexes, such as those of ruthenium, rhodium, iridium, and nickel are also highly active catalysts in the catalytic functionalization of CÀH bonds. [11] Herein, we report on the Ru 2 + -catalyzed arylation of C À H bonds in 2-arylpyridine derivatives with diaryliododium salts.…”

“…The reaction is compatible with a wide range of functional groups. Although diaryliodonium salts have been commonly used as arylation reagent in Pd-and Cu-catalyzed arylation of CÀH bonds, [7,8] only two examples of the Ru-catalyzed arylation of CÀH bonds have appeared in the literature. [9] However, these reactions proceed by a radical mechanism because irradiation is required.…”