Borirenes and Boriranes: Development and Perspectives

Abstract

Strained compounds constitute a highly topical area of research in chemistry. Borirene and borirane both feature a BC2 three‐membered ring. They can be viewed as the structural analogues of cyclopropane and cyclopropene, where a CH2 unit of the carbonaceous counterparts is replaced with BH, respectively. Indeed, this structural variation introduces numerous intriguing aspects. For instance, borirane and borirene are both Lewis acidic due to the presence of a tricoordinate borane center. In addition, borirene is 2π aromatic according to Hückel's rule. In addition to their ability to form adducts with Lewis bases and the capacity of borirenes to act as ligands in coordination with metals, both borirenes and boriranes exhibit ring‐opening reactivity due to the considerable ring strain. Under specific conditions, coordinated boriranes can even cleave two BC bonds to serve as formal borylene sources (although the reaction mechanisms are quite complex). On the other hand, recent successful syntheses of benzoborienes and their carborane‐based three‐dimensional analogues (also referred to as carborane‐fused boriranes) have introduced novel perspectives to this field. For instance, they display excellent ring‐expanding reactivity, possibly attributed to the boosted ring strain arising from the fusion of borirenes with benzene and boriranes with o‐carborane. Importantly, their applications as valuable “BC2” synthons have become increasingly evident along with the newly disclosed reactivity. Additionally, the boosted Lewis acidity of carborane‐fused boriranes, thanks to the potent electron‐withdrawing effect of o‐carborane, combined with their readiness for ring enlargement, makes them promising candidates as electron‐accepting building blocks in the construction of chemically responsive luminescent materials. This review provides a summary of the synthesis and reactivity of borirene and borirane derivatives, with the aim of encouraging the design of new borierene‐ and borirane‐based molecules and inspiring further exploration of their potential applications.

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

“…On the other hand, borirenes 17–24 and boriranes 8,9,24–35 have gained attention due to their unique electronic and structural features. 36 Typically, these small boracycles can undergo ring-opening reactions under irradiation 22 or thermal conditions, 26–29 or when reacting with polar bonds. 22,23,30,31 However, it should be noted that their application in synthesis remains somewhat limited.…”

“…Most importantly, it has become evident that they can be applied as “C 2 B” synthons for organic and organometallic synthesis. 36 It is noteworthy that, despite extensive research, their reactivity towards organic azides has not yet been reported.…”