Mallory-Type Reactivity of 1,2-Dihydroazaborinines: 6π-Electrocyclization-[1,5]‑H Shift Cascade toward BN-Doped Polycyclic Frameworks
Sonja M. Biebl, Robert C. Richter, Markus Ströbele, Ivana Fleischer, Holger F. Bettinger
TL;DR
This paper explores the unique chemical reactions of 1,2-dihydroazaborinines to form BN-doped polycyclic frameworks through a cascade of photochemical processes.
Contribution
The study introduces a novel cascade reaction involving 6π-electrocyclization and [1,5]-hydrogen shift to selectively synthesize BN-doped polycyclic frameworks.
Findings
1,2-Dihydroazaborinines undergo photochemistry to form Dewar or benzvalene isomers depending on substitution.
An o-BN-terphenyl framework forms via 6π-electrocyclization and rearomatizes through a [1,5]-hydrogen shift.
Oxidative conditions yield a BN-incorporated triphenylene, demonstrating selective synthesis of BN-doped frameworks.
Abstract
1,2-Dihydro-1,2-azaborinines exhibit highly selective substitution-dependent photochemistry, yielding either Dewar or benzvalene isomers. Through targeted substitution, an o-BN-terphenyl framework is constructed, which undergoes 6π-electrocyclization upon irradiation. The resulting BN-polyenes rearomatize spontaneously via a [1,5]-hydrogen shift. Under oxidative conditions, an unprecedented BN incorporated triphenylene results. By rationally tuning substitution and reaction conditions, this pathway is favored over Dewar isomer formation, offering selective routes to BN-doped polycyclic frameworks from multiphotoresponsive precursors.
Genes, proteins, chemicals, diseases, species, mutations and cell lines named across the full text — each resolved to its canonical identifier and authoritative record.
Click any figure to enlarge with its caption.
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8Peer Reviews
No public reviews on file for this paper yet. If you reviewed it on a platform where reviews are public (OpenReview, ICLR, NeurIPS, ICML), you can paste yours below so the community can read it here.
Videos
No videos yet. Explain this paper in a talk, walkthrough, or lecture? Add one.
Taxonomy
TopicsOrganoboron and organosilicon chemistry · Radical Photochemical Reactions · Catalytic C–H Functionalization Methods