Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes. Issue 7 (18th July 2017)

• Record Type: Journal Article
• Authors: Marshall, Jonathan L.; Lehnherr, Dan; Lindner, Benjamin D.; Tykwinski, Rik R.
• Is Part Of: ChemPlusChem. Volume 82:Issue 7(2017)
• Page Start: 967
• Page End: 1001
• Publication Date: 2017-07-18
• Subjects: acenes -- cumulenes -- indenofluorenes -- polycyclic aromatic hydrocarbons -- reductive elimination; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201700168
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: Acenes, heteroacenes, conjugated polycyclic hydrocarbons, and polycyclic aromatic hydrocarbons (collectively referred to in this review as conjugated polycyclic molecules, CPMs) have fascinated chemists since they were first isolated and synthesized in the mid 19th century. Most recently, these compounds have shown significant promise as the active components in organic devices (e.g., solar cells, thin‐film transistors, light‐emitting diodes, etc.), and, since 2001, a plethora of publications detail synthetic strategies to produce CPMs. In this review, we discuss reductive aromatization, reductive dearomatization, and elimination/extrusion reactions used to form CPMs. After a brief discussion on early methods to synthesize CPMs, we detail the use of reagents used for the reductive (de)aromatization of precursors containing 1, 4‐diols/diethers, including SnCl2 and iodide (I − ). Extension of these methods to carbomers and cumulenes is briefly discussed. We then describe low‐valent metal species used to reduce endoxides to CPMs, and discuss the methods to directly reduce acenediones and acenones to the respective acene. In the final section, we describe methods used to affect aromatization to the desired CPM via extrusion of small, volatile molecules. Abstract : Completing circuits : Conjugated polycyclic molecules play a central role in most functional organic materials. Established routes to these valuable compounds rely on reductive aromatization, dearomatization, and elimination reactions which are reviewed (see figure).