Anthranilamide: A Simple, Removable ortho-Directing Modifier for Arylboronic Acids Serving also as a Protecting Group in Cross-Coupling Reactions

Abstract

Anthranilamide (AAM) serves as a bifunctional modifier on the boron atom in catalytic transformations of arylboronic acids. It makes boronyl groups unreactive in Suzuki-Miyaura coupling and promotes Ru-catalyzed ortho-silylation. Suzuki-Miyaura coupling of AAM-modified bromophenylboronic acids with tolylboronic acid gave 1,1'-biaryl-4-boronic acid bearing AAM on the boron atom, which subsequently underwent Ru-catalyzed ortho-silylation at the 3-position by virtue of the ortho-directing effect of the AAM group.

An Efficient Ni/Pd Catalyzed Chemoselective Synthesis of 1,3,2‐Benzodiazaborininones from Boronic Acids and Anthranilamides

“…[7] On the basis of above results and previous reports, [15] a plausible mechanism is illustrated in Scheme 5. Treatment of 3 i with (4-(tert-butyl)phenyl) boronic acid in THF in the presence of PdCl 2 /NiBr 2 (PPh 3 ) 2 and K 3 PO 4 at room temperature successfully afforded the cross-coupling product 6 in 82% yield (Scheme 5).…”

“…[5] In addition, since the BÀ N unit has a strong dipole moment, replacing the C=C with a BÀ N unit can reduce the HOMO-LUMO gap, which usually results in a chemiluminescent material. [7] These compounds with an anthranilamide (aam) substituent on the boron center [ArÀ B(aam)] are temporarily masked for their reactivity toward transmetalation, and have proven to be useful reagents in Suzuki-Miyaura cross-coupling reaction. [7] These compounds with an anthranilamide (aam) substituent on the boron center [ArÀ B(aam)] are temporarily masked for their reactivity toward transmetalation, and have proven to be useful reagents in Suzuki-Miyaura cross-coupling reaction.…”

Sequential and iterative Pd-catalyzed cross-coupling reactions in organic synthesis

“…Other boronic acid derivatives can be coupled in the presence of boronic amides due to their reduced Lewis acidity at the boron [52, 53]. Lone-pair donation from the Lewis basic nitrogen makes the boronic amide very unreactive under basic coupling conditions.…”

Anthranilamide-masked o-Iodoarylboronic Acids as Coupling Modules for Iterative Synthesis of ortho-Linked Oligoarenes

“…10 In addition to the o-silylboronic acids 2a, 2b, 2d, 2g, and 2k reported in the previous paper, we also synthesized new derivatives in good yields from the corresponding AAM-protected arylboronic acids (Table 1). Iododesilylation was accomplished efficiently by use of ICl at a low temperature.…”

“…10 We envisioned that AAMprotected o-haloarylboronic acids 3 may serve as highly convenient building modules in the synthesis of helical oligo(o-arene)s via iterative SuzukiMiyaura cross-coupling ( Figure 1). The modules 3 may be obtained directly by halodesilylation of AAM-protected o-silylarylboronic acids 2, which in turn are conveniently prepared by o-silylation of AAMprotected arylboronic acids 1.…”