Zirconacyclopentadiene‐Annulated Polycyclic Aromatic Hydrocarbons

Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don

doi:10.1002/anie.201700818

Zirconacyclopentadiene‐Annulated Polycyclic Aromatic Hydrocarbons

Journal Article · Thu Mar 23 00:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201700818· OSTI ID:1401284

^[1]; ^[1]; Tilley, T. Don ^[1]

Department of Chemistry University of California Berkeley CA 94720 USA

Abstract

Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low‐valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high‐yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X‐ray crystallography) of PAHs containing one or more appended dienes with the ortho‐quinodimethane (o‐QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels–Alder reactions.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1401284

Alternate ID(s):: OSTI ID: 22599371

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 17 Vol. 56; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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