Boroles from alumoles: accessing boroles with alkyl-substituted backbones via transtrielation.

The alumole Cp3tAlC4Et4 (Cp3t = 1,2,4-tris(tert-butyl)cyclopentadienyl) is reported to be capable of transferring its butadiene moiety to aryl(dihalo)boranes to generate boroles through aluminum-boron exchange. The products feature a rare alkyl-substituted backbone, which, as shown in other examples, often leads to dimerization due to insufficient steric protection of the antiaromatic borole ring. Sterically crowded aryl groups bound to the boron atom are shown to prevent dimerization, allowing access to the first monomeric derivatives of this type. Results from UV-vis spectroscopy, electrochemistry, and DFT calculations reveal that the alkyl substituents cause remarkable modifications in the optical and electronic properties of the boroles compared to their perarylated counterparts.

Azide-alkyne cycloadditions with an electronically activated alkyne: indole formation via 1-aryl-1,2,3-triazole-derived imino carbenes.

We report that the use of a diaminoalkyne in the azide-alkyne cycloaddition with aryl azides leads to 3H-indoles under mild, uncatalysed conditions. Computations reveal that N2 extrusion from, in one case, isolable triazoles is facile, generating imino carbenes, which undergo intramolecular aryl C-H bond activation and give 3H-indoles as products.

Synthesis of novel six-, seven- and eight-membered aluminum-containing rings by alumole ring expansion.

The chemistry of aluminacyclopentadienes, also known as alumoles, has experienced a resurgence in recent years, resulting in the preparation of a number of new entries in this class of compound. In contrast, their reactivity remains relatively unexplored. Thus far, their Lewis acid-base chemistry has been studied, as well as various ring-insertion reactions with unsaturated species such as alkynes and azides. Herein we present a range of new ring expansion reactions of an alumole with heteroatom-containing unsaturated species, providing novel six-, seven- and eight-membered cyclic products with high heteroatom content. Additionally, an unusual reaction was observed when the alumole was treated with morpholine-N-oxide, involving a stepwise insertion of two oxygen atoms, first into the exocyclic Al-C bond and then the endocyclic Al-C bond.

Synthesis, structure and insertion reactivity of Lewis acidic 9-aluminafluorenes.

9-Aluminafluorenes have only been sparingly investigated and their properties still remain largely unexplored. Herein, we report the synthesis of five aluminafluorene derivatives with a diverse array of aluminium substituents and probe their Lewis acid properties and reactivity. We show that 9-bromo-9-aluminafluorene readily forms Lewis acid-base adducts with N-heterocyclic carbenes (NHCs), cyclic (alkyl)(amino)carbenes (CAACs) and pyridines and that it undergoes a selective ring expansion reaction with the iminoborane tBuN[triple bond, length as m-dash]BMes to give a seven-membered ring, which can be viewed as a boron-nitrogen analogue of alumepins.

Ring expansion of alumoles with organic azides: selective formation of six-membered aluminum-nitrogen heterocycles.

Aside from simple Lewis acid-base chemistry, the reaction chemistry of aluminacyclopentadienes, which are commonly referred to as aluminoles or simply alumoles, remains relatively underdeveloped. To date, few attempts to extend their inherent insertion and cycloaddition reactivity to the construction of stable aluminum-containing heterocycles have been reported. Herein, we demonstrate the selective ring expansion of a cyclopentadienyl-substituted alumole with a series of organic azides to form unsaturated six-membered AlN heterocycles. Depending on the substituent on the azide, the reaction proceeds either with or without loss of dinitrogen, leading to incorporation of only the "NR" unit of the azide or the entire azo substituent into the periphery of the heterocycle. A deeper understanding of these ring expansion reactions is reached through computational studies, illustrating deviations in the mechanism as a function of the organic azide employed.

Reduction of a dihydroboryl cation to a boryl anion and its air-stable, neutral hydroboryl radical through hydrogen shuttling.

The addition of Lewis bases to a cyclic (alkyl)(amino)carbene (CAAC)-supported dihydroboron triflate yields the mixed doubly base-stabilised dihydroboryl cations [(CAAC)BH2L]+. Of these, [(CAAC)2BH2]OTf (OTf = triflate) underwent facile two-electron reduction with KC8 owing to a 1,2-hydride migration from boron to the carbene carbon to yield a stable hydroboryl anion. One-electron oxidation of the latter yielded the first neutral hydroboryl radical, which is bench-stable in the solid state.

A New Class of Neutral Boron-Based Diradicals Spanned by a Two-Carbon-Atom Bridge.

A new structural class of boron-based diradicals is prepared by Lewis base addition to and reduction of singly cyclic (alkyl)(amino)carbene (CAAC) stabilised diborylalkenes. The diradicals feature a perpendicular olefinic bridge preventing delocalization between the B(CAAC) π systems, making the coupling between the spin centres very weak. DFT calculations indicate that the compounds are ground-state (open-shell) singlets, with triplet states negligibly higher in energy, thus making the triplet states easily populated thermally.