Boron–nitrogen heteroarenes hold great promise for practical application in many areas of chemistry. Enduring interest in realizing this potential has in turn driven perennial innovation with respect to these compounds’ synthesis. This Perspective discusses in detail the most recent advances in methods pertaining to the preparation of BN-isosteres of benzene, naphthalene, and their derivatives. Additional focus is placed on the progress enabled by these syntheses toward functional utility of such BN-heterocycles in biochemistry and pharmacology, materials science, and transition-metal-based catalysis. The prospects for future research efforts in these and related fields are also assessed.

/pdf/the-state-of-the-art-in-azaborine-chemistry-new-synthetic-1suoynzkgt.pdf

The State of the Art in Azaborine Chemistry: New Synthetic Methods and Applications.

The development of helicene molecules with significant chiroptical responses covering a broad range of the visible spectrum is highly desirable for chiral optoelectronic applications; however, their absorption dissymmetry factors (gabs) have been mostly lower than 0.01. In this work, we report unprecedented B,N-embedded double hetero[7]helicenes with nonbonded B and N atoms, which exhibit excellent chiroptical properties, such as strong chiroptical activities from 300 to 700 nm, record high gabs up to 0.033 in the visible spectral range, and tunable circularly polarized luminescence (CPL) from red to near-infrared regions (600-800 nm) with high photoluminescence quantum yields (PLQYs) up to 100%. As revealed by theoretical analyses, the high gabs values are related to the separate molecular orbital distributions owing to the incorporation of nonbonded B and N atoms. The new type of B,N-embedded double heterohelicenes opens up an appealing avenue to the future exploitation of high-performance chiroptical materials.

B,N-Embedded Double Hetero[7]helicenes with Strong Chiroptical Responses in the Visible Light Region.

The intramolecular C-H borylation of (hetero)arenes and alkenes using electrophilic boranes is a powerful transition metal free methodology for forming C-B bonds. These C-H borylation reactions are preceded by intermolecular bond (both dative and covalent) formation, with examples proceeding via initial C-B and N-B bond formation dominating this field thus both are discussed in depth herein. Less prevalent intramolecular electrophilic C-H borylation reactions that proceed by intermolecular O-B, S-B and P-B bond formation are also summarised. Mechanistic studies are presented that reveal two mechanisms for C-H borylation, (i) electrophilic aromatic substitution (prevalent with B-X electrophiles); (ii) σ-bond metathesis mediated (prevalent with B-H and B-R electrophiles). To date, intramolecular electrophilic C-H borylation is utilised mainly for accessing boron containing conjugated organic materials, however recent developments, summarized herein alongside early studies, have highlighted the applicability of this methodology for forming synthetically versatile organo-boronate esters and boron containing bioactives. The multitude of synthetic procedures reported for intramolecular electrophilic C-H borylation contain many common features and this enables key requirements for successful C-H borylation and the factors effecting regioselectivity and substrate scope to be identified, discussed and summarized.

/pdf/intramolecular-directed-electrophilic-c-h-borylation-1mmtkv5ge2.pdf

Intramolecular (directed) electrophilic C-H borylation

BN/CC isosterism has emerged as a viable strategy to expand the chemical space of organic molecules. In particular, the application of BN/CC isosterism to arenes has received significant attention due to the vast available chemical space provided by aromatic hydrocarbons. The synthetic efforts directed at assembling novel aromatic BN heterocycles have resulted in the discovery of new properties and functions in a variety of fields including biomedical research, medicinal chemistry, materials science, catalysis, and organic synthesis. This tutorial review specifically covers recent advances in synthetic technologies that functionalize assembled boron-nitrogen (BN) heterocycles and highlights their distinct reactivity and selectivity in comparison to their carbonaceous counterparts. It is intended to serve as a state-of-the-art compendium for readers who are interested in the reaction chemistry of BN heterocycles.

/pdf/late-stage-functionalization-of-bn-heterocycles-41yzintfsp.pdf

Late-stage functionalization of BN-heterocycles

The least stable isomer of the parental BN naphthalene series has been synthesized in a simple four-step sequence. Its experimental electronic structure characterization via UV-PES, cyclic voltammetry, and UV–vis spectroscopy in direct comparison with three other known BN naphthalene isomers has established two guiding principles for predicting the electronic structures of BN acene compounds: (1) Orientational BN isomers have similar HOMO–LUMO gaps. (2) For each pair of orientational BN isomers, the more thermodynamically stable compound has the lower HOMO energy. Furthermore, we demonstrate that BN/CC isosterism in the context of BN-9,1-Naph can impact crystal packing to favor a cofacial π-stack motif.

The Least Stable Isomer of BN Naphthalene: Toward Predictive Trends for the Optoelectronic Properties of BN Acenes

Considerable efforts have been devoted to achieving stable acene derivatives for electronic applications; however, the instability is still a major issue for such derivatives. To achieve higher stability with minimum structural change, CC units in the acenes were replaced with isoelectronic BN units to produce a novel BN-embedded tetrabenzopentacene (BNTBP). BNTBP, with a planar structure, is highly stable to air, moisture, light, and heat. Compared with its carbon analogue tetrabenzopentacene (TBP), BN embedment lowered the highest occupied molecular orbital (HOMO) energy level of BNTBP, changed the orbital distribution, and decreased the HOMO orbital coefficients at the central carbon atoms, which stabilize BNTBP molecules upon exposure to oxygen and sunlight. The single-crystal microribbons of BNTBP exhibited good performance in field-effect transistors (FETs). The high stability and good mobility of BNTBP indicates that BN incorporation is an effective approach to afford stable large-sized acenes with desired properties.

BN‐Embedded Tetrabenzopentacene: A Pentacene Derivative with Improved Stability

Efficient Modular Synthesis of Substituted Borazaronaphthalene

BN Fused Diazulenyl‐Carbazole: Synthesis, Structure, and Properties

We report a novel synthetic route of BN-benzo[b]triphenylene (BNBT) with a key-step yield exceeding 90% based on simple raw materials. The solvent effect on the optical absorption and fluorescence of BNBT is examined, and a linear relationship between the Stokes shift (ΔνS) and the solvent parameters {α, β, π*} is generalized. The fluorescence lifetime correlates positively with the fluorescence quantum yield, which is about 10 folds of benzo[b]triphenylene (BT) as a structural counterpart (66% vs 6%). Moreover, the quantum yield of triplet-excited state BNBT is shown to be as low as a few thousandths. 

Qi‐Ran Chen

Papers

BN‐Embedded Tetrabenzopentacene: A Pentacene Derivative with Improved Stability

Efficient Modular Synthesis of Substituted Borazaronaphthalene

BN Fused Diazulenyl‐Carbazole: Synthesis, Structure, and Properties

Synthesis and photophysical properties of BN-benzo[b]triphenylene