Structure-constraint induced increase in Lewis acidity of tris(-carboranyl)borane and selective complexation with Bestmann ylides.

The Lewis acidity of tris(-carboranyl)borane has been slightly increased by mimicking the structural evolution from triarylborane to 9-aryl-9-borafluorene. The -carborane-based analogue (CBH)B(CBH), obtained salt elimination between LiCBH and (CBH)BBr, has been fully characterized. Gutmann-Beckett and computational fluoride/hydride ion affinity (FIA/HIA) studies have confirmed the increase in Lewis acidity, which is attributable to structural constraint imposed by the CC-coupling between two carboranyl groups.

Correction: Reactivity study of Lewis superacidic carborane-based analogue of 9-bromo-9-borafluorene towards Lewis bases.

Correction for 'Reactivity study of Lewis superacidic carborane-based analogue of 9-bromo-9-borafluorene towards Lewis bases' by Libo Xiang , , 2024, , 11655-11658, https://doi.org/10.1039/D4DT01615G.

Reactivity study of Lewis superacidic carborane-based analogue of 9-bromo-9-borafluorene towards Lewis bases.

In this contribution, we present the reactions of the -carborane-based analogue of 9-bromo-9-borafluorene, a Lewis superacid, with diverse Lewis bases. A range of acid-base adducts, along with an intramolecular C-H activation product, were generated. All new compounds have been fully characterized.

Avenue to novel -carboranyl boron compounds - reactivity study of -carborane-fused aminoborirane towards organic azides.

Herein we report the reactivity study of -carborane-fused bis(trimethylsilyl)aminoborirane towards three different types of organic azides, , aryl, alkyl, and silyl azides. The reaction with ArN (Ar = 2,6-iPrCH, 2,6-CHCl, 2,4,6-CHBr, CF) resulted in the cycloaddition of ArN to the borirane BN unit accompanied by silyl migration. Conversely, in the reaction with BnN, only the BnN : borirane 1 : 2 ring expansion product was obtained.

A bottleable super-electron-donor for catalytic borylation of aryl halides.

[(Dpp-bian)B(DMAP)] (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, DMAP = 4-(dimethylamino)pyridine), a bottleable super electron donor (SED), was demonstrated to serve as a SED catalyst in the borylation of aryl iodides, bromides, and the more challenging chlorides. Apart from installing Bpin from Bpin, the SED-catalyzed borylation protocol is also applicable for installing Bdan from Bpin-Bdan. The radical mechanism has been confirmed by the radical trapping and radical clock experiments.