Ethynyl-B(dan) in [3+2] Cycloaddition and Larock Indole Synthesis: Synthesis of Stable Boron-Containing Heteroaromatic Compounds.

The cycloaddition of nitrile oxides with ethynyl-B(dan) (dan=naphthalene-1,8-diaminato) allowed the facile preparation of diverse isoxazolyl-B(dan) compounds, all of which displayed excellent protodeborylation-resistant properties. The dan-installation on the boron center proves vital to the high stability of the products as well as the perfect regioselectivity arising from hydrogen bond-directed orientation in the cycloaddition. The diminished boron-Lewis acidity of ethynyl-B(dan) also renders it amenable to azide-alkyne cycloaddition, Larock indole synthesis and related heteroannulations. The obtained boron-containing triazole, indoles, benzofuran and indenone exhibit sufficient resistance toward protodeborylation. Despite the commonly accepted transmetalation-inactive property derived from the diminished Lewis acidity, the synthesized heteroaryl-B(dan) compound was still found to be convertible to the oligoarene via sequential Suzuki-Miyaura coupling.

Stable Silapyramidanes.

Starting from tetrakis(trimethylsilyl)cyclobutadiene and an amidinate-supported silylene of the Roesky-type, a sequence of addition and reduction cleanly gives the elusive silapyramidane via an isolable cyclobutene intermediate with an exocyclic Si═C bond. The silapyramidane features an unusually shielded 29Si NMR resonance at -448.3 ppm for the apex silicon atom. Treatment with Fe2(CO)9 results in the formation of the corresponding silapyramidane-iron complex. Silapyramidane also reacts with the cyclobutadiene starting material to cleanly afford a fluorescent spirobis(silole).

Complexation-Triggered Fluctuation of π-Conjugation on an Antiaromatic Dicyanoanthracene Dianion.

The formation of Lewis pairs is an important chemical concept. Recently, the complexation of Lewis acidic tris(pentafluorophenyl)borane with Lewis basic moieties and subsequent reduction has emerged as a fascinating strategy for designing novel reactions and structures. The impact of the complexation and subsequent reduction of antiaromatic systems bearing Lewis base moieties has been investigated. We found how Lewis adduct formation stabilizes an antiaromatic system consisting of 9,10-dicyanoanthracene and tris(pentafluorophenyl)borane by using synthesis, X-ray crystallography, spectroscopic analysis, and quantum chemical calculations.

Surefire generation of stannylpotassium: highly reactive stannyl anions and applications.

Organometallic reagents such as organolithium and Grignard reagents have long been esteemed in chemical synthesis for their exceptional reactivity. In contrast, the application of their sodium and potassium counterparts has been comparatively sluggish, notwithstanding their augmented reactivity stemming from their heightened ionic character. This inertia persists due to the constrained accessibility of these heavy alkali metal reagents. In this study, our focus was directed towards devising a convenient and pragmatic approach for fabricating heavy alkali metal-based reagents, particularly those grounded in potassium. Herein, we present a novel, direct method for generating stannylpotassium (Sn-K) reagents through the simple combination of readily available silylstannanes and t-BuOK. Subsequently, the generated Sn-K reagents were effectively harnessed for stannylative substitution of aryl halides, furnishing an array of arylstannanes straightforwardly under transition metal-free conditions. This application distinctly underscores the potential utility of highly reactive Sn-K species, hitherto sparingly tapped into within the realm of synthetic organic chemistry. Furthermore, our investigation confirms that Sn-K reagents manifest notably superior reactivity compared with their well-established stannyllithium (Sn-Li) counterparts. This heightened reactivity can be ascribed to the increasing ionic character of Sn-K, which was supported by computational experiments.