Ruthenium‐ and Rhodium‐Catalyzed Dehydrogenative ortho‐Alkenylation of Benzylamines via Free Amino Group Directed CH Bond Cleavage

Abstract

The dehydrogenative direct coupling of a,a-disubstituted benzylamines with acrylates takes place efficiently at room temperature under ruthenium catalysis, accompanied by free amino groupdirected ortho-alkenylation and successive cyclization to produce (isoindol-1-yl)acetic acid derivatives. The reactions using styrenes in place of acrylates proceed effectively in the presence of a rhodium catalyst rather than ruthenium.

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[111][112][113][114][115] Therefore,m ajor studies have focused on amine functionalization either by protection or by installing adirecting group on the amino function. This can be attributed to the high reactivity of amines towards various reagents and their strong coordinating ability towards am etal center, which makes them inconvenient for use in ac atalytic reaction.…”

“…This can be attributed to the high reactivity of amines towards various reagents and their strong coordinating ability towards am etal center, which makes them inconvenient for use in ac atalytic reaction. [111][112][113][114][115] Therefore,m ajor studies have focused on amine functionalization either by protection or by installing adirecting group on the amino function. Although the major focus of this Review is on directed CÀHf unctionalization, we also summarize our current knowledge on the CÀHfunctionalization of amines where ad irecting group is installed on the amino function.…”

Ruthenium‐Catalyzed Synthesis of Heterocycles via CH Bond Activation

“…Under ruthenium catalysis, oxidative coupling of , -disubstituted benzylamines with acrylates can be performed efficiently at room temperature to produce (isoindol-1-yl)acetic acid derivatives (Eq. (7.48)) [58]. The reaction takes place accompanied by free amino group-directed ortho-alkenylation and successive intramolecular cyclization.…”

Rh‐Catalyzed Synthesis of Nitrogen‐Containing Heterocycles

“…(5.11)). It is rare for catalytic processes to use an amino group as a directing group [9]. The reaction was unsuccessful when styrene was used as the coupling partner.…”