ChemInform Abstract: Asymmetric Dearomatization of 1‐Aminonaphthalene Derivatives Through C—C Bond Formation with Electron‐Rich Heterocycles as Nucleophiles.

Abstract

The gold catalyzed asymmetric intramolecular C—C bond forming reaction of 1‐aminonaphthalene derivatives provides access to pentacyclic heterocycles with low to moderate enantioselectivities.

Platinum-Catalyzed Intramolecular Spirocyclization of N-(Methylnaphthalenyl)propiolamides via Formal Aromatic Ene Reaction

“…14 When using N-benzyl-N-(naphthalen-1yl)propiolamides and a cationic platinum(II) complex, the catalytic dearomative intramolecular 6-endo cyclization through CC bond formation at the ipso and ortho positions of the acylamino group proceeded in high yields (Figure 2a, bottom). 15,16 In this paper, we disclose the platinum(II)catalyzed intramolecular dearomative spirocyclization (5-endo cyclization) of N-(methylnaphthalenyl)propiolamides via the deprotonation−protonation sequence [formal aromatic ene reaction (Figure 2b)]. Importantly, in this transformation, the naphthyl and electron-rich aryl groups are compatible and no dearomative intramolecular 6-endo cyclization products were generated, which are in contrast to the previously reported iodinative spirocyclization 7 and CC bond-forming dearomatization, respectively.…”

“…Importantly, in this transformation, the naphthyl and electron-rich aryl groups are compatible and no dearomative intramolecular 6-endo cyclization products were generated, which are in contrast to the previously reported iodinative spirocyclization 7 and CC bond-forming dearomatization, respectively. 15,16 We first investigated the reaction of N-(1-methylnaphthalen-2-yl)propiolamide 1a in the presence of π-electrophilic reagents at room temperature (Table 1). Although no reaction was observed by using a cationic palladium(II)/rac-binap catalyst (entry 1), the use of a cationic platinum(II)/rac-binap catalyst 17 afforded dearomative spirocyclization product 2a in 64% yield (entry 2).…”