Nickel‐catalyzed C−H bond Alkoxylation of Amides with Alcohols

Abstract

An efficient Nickel‐catalyzed C−H bond alkoxylation of benzamides and olefinic carboxamides with alcohols were achieved for the first time using bidentate auxiliary. We demonstrated high‐functional group compatibility and tolerates wide‐range of alcohols.

Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

“…There are several methods available for removing this auxiliary, including hydrolysis under acidic conditions (Scheme a) , or basic conditions (Scheme b), , alcoholysis under acidic conditions using BF 3 ·Et 2 O in MeOH (Scheme c), Boc-protection followed by amide cleavage using LiOH/H 2 O 2 (Scheme d), , oxidative cleavage by ceric ammonium nitrate (CAN) (Scheme e), oxidative cleavage via ozonolysis followed by cleavage (Scheme f,g) or amide (Scheme g), and Ni-catalyzed alcoholysis (Scheme h) . The availability of several synthetic methodologies for the removal of an 8-aminoquinoline auxiliary enhances the synthetic utility of this directing group for the formation of C–C bonds and C–heteroatom bonds. − The use of an 8-AQ directing group for the construction of C–C bonds via C–H bond activation is included here.…”

Advances in Transition-Metal-Catalyzed C–H Bond Oxygenation of Amides

“…The advantage of the 8-aminoquinolinyl chelation assistance has been implemented in the nickel-catalyzed C-H bond alkoxylation by Sundararaju and Rajesh (Scheme 8). 22 Thus, a Ni(OAc) 2 •4H 2 O/AdCOOH catalyst system efficiently catalyzed the C-H alkoxylation of benzamides derivatives with aliphatic alcohols via bidentate-chelation assistance.…”

Nickel‐mediated Ortho C(sp2)−H Alkoxylation of Amides

“…However, low‐priced metal as promoter during C−O bond forming process is still less reported [8b,d,e] . As far as we know, nickel as a promising promotor has been less reported in alkoxylation or acetoxylation [10] …”