Dearomative Cyclopropanation of Naphthols via Cyclopropene Ring‐Opening

Abstract

The dearomatization of 2‐naphthols represents a simple method for the construction of complex 3D structures from simple planar starting materials. We describe a cyclopropanation of 2‐naphthols that proceeds via cyclopropene ring‐opening using rhodium and acid catalysis under mild conditions. The vinyl cyclopropane molecules were formed with high chemoselectivity and scalability, which could be further functionalized at different sites. Both computational and experimental evidence were used to elucidate the reaction mechanism.

Reactivity of quinone methides with carbenes generated from α-diazocarbonyl compounds and related compounds

“…Recently, Lautens's group reported the rhodium and camphorsulfonic acid (CSA)-catalyzed dearomative cyclopropanation of 2-naphthol compounds via cyclopropene ring-opening, involving initial carbene insertion, followed by water elimination. 32 The ring-opening of cyclopropene 33 107 derivatives in the presence of a rhodium catalyst (Rh 2 (OAc) 4 ) delivered rhodium carbene compounds. Thus, they reacted with (1-hydroxyalkyl)-naphthalene-2-ol compounds 108 in a dearomative fashion to deliver a variety of vinyl cyclopropane compounds 109, in the presence of CSA and MgSO 4 , with good Based on control experiments, the observed products, and DFT calculations, the product formation could be explained via two pathways.…”

Dearomatization [4+2] Cycloaddition of Nonactivated Benzene Derivatives

“…Dearomatization reactions, one of the important branches of the transformations of aromatic compounds, have seen significant expansion and refinement in recent years with a steady increase in the number of dearomatization methods, providing new synthetic approaches to more complex, high-value building blocks and natural products . Nevertheless, most of the advancements have largely been limited to specific classes of activated arenes, such as arenols, naphthylamines, and heteroarenes . The dearomatization methods for utilizing simple and nonactivated benzene derivatives are significantly limited …”