Synthesis of ortho-Diamino-Functionalized 1-Arylnaphthalenes through Nickel-Catalyzed Cyclization of Ynamide-Benzylnitriles with Organoboronic Acids

Abstract

A nickel-catalyzed highly regioselective addition/cyclization of ynamide-benzylnitriles with organoboronic acids has been developed. The reaction offers an attractive route for the construction of diamino-functionalized 1-arylnaphthalenes, which is difficult to synthesize by other methods. In addition, a wide range of functional groups are tolerated in this reaction.

Recent Progress in Arylmetalative Cyclization/Annulation of Functionalized Alkynes with Organoboranes

“…anti ‐Arylmetalative cyclization on specifically designed alkynes affords unusual architectures with cyclic endo ‐alkene derivatives [39–55] . In this realm, Tsukamoto group discovered the abnormal trans ‐addition of organoboronic reagents on alkynals and alkynones using palladium(0) catalyst [38] .…”

“…anti-Arylmetalative cyclization on specifically designed alkynes affords unusual architectures with cyclic endo-alkene derivatives. [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55] In this realm, Tsukamoto group discovered the abnormal trans-addition of organoboronic reagents on alkynals and alkynones using palladium(0) catalyst. [38] The proposed mechanism involved oxidative addition without nucleometalation (without orthogonal activation of alkyne by Pd complex).…”

Metal-catalyzed reactions of organic nitriles and boronic acids to access diverse functionality

“…Very recently in 2021, Liu's group also developed the synthesis of ortho-diamino functionalized 1-arylnaphthalenes ( 52) via a Ni(II)-catalyzed regioselective addition/cyclization of ynamide-benzylnitriles (51) with organoboronic acids (Scheme 24). 42 This strategy provides an attractive route to access diamino-functionalized 1-arylnaphthalenes. The reaction proceeds through a regioselective β-addition of arylnickel species to the ynamide followed by cis-trans isomerization and, finally, a nucleophilic attack of the resulting alkenylmetal on the tethered nitrile group to afford the corresponding products.…”

Gold(I)‐Catalyzed and PTSA‐Promoted Cycloisomerization of Ynamides to Access Pyrrole Substituted α,β‐Unsaturated Ketones**

“…[5] In addition, selected examples of metal-assisted cyclization reaction via polarity inversion of CÀ C triple bond are fantastic addition to the ynamide chemistry. [6][7][8] Notably, Lam and Ye groups independently reported that reversal of CÀ C triple bond polarity in ynamides is possible by metal catalysts and arylboronic acids. [7] In another report, Sahoo group entrenched a gold(I)-catalyzed umpolung cycloisomerization of yne-teth-the background study, we realized that the chemistry of ynetethered ynamides is emerging but still in its infancy.…”

“…Of late, the asymmetric version of this reaction was developed by Marinetti, Arnold, and co‐workers [5] . In addition, selected examples of metal‐assisted cyclization reaction via polarity inversion of C−C triple bond are fantastic addition to the ynamide chemistry [6–8] . Notably, Lam and Ye groups independently reported that reversal of C−C triple bond polarity in ynamides is possible by metal catalysts and arylboronic acids [7] .…”