A Sequential Cyclization/π-extension Strategy for Modular Construction of Nanographenes Enabled by Stannole Cycloadditions

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Jun 13

PMID 35694352

Authors

Harrison M Bergman

D Dawson Beattie

Gavin R Kiel

Rex C Handford

Yi Liu

T Don Tilley

Affiliations

Soon will be listed here.

Abstract

The synthesis of polycyclic aromatic hydrocarbons (PAHs) and related nanographenes requires the selective and efficient fusion of multiple aromatic rings. For this purpose, the Diels-Alder cycloaddition has proven especially useful; however, this approach currently faces significant limitations, including the lack of versatile strategies to access annulated dienes, the instability of the most commonly used dienes, and difficulties with aromatization of the [4 + 2] adduct. In this report we address these limitations the marriage of two powerful cycloaddition strategies. First, a formal CpZr-mediated [2 + 2 + 1] cycloaddition is used to generate a stannole-annulated PAH. Secondly, the stannoles are employed as diene components in a [4 + 2] cycloaddition/aromatization cascade with an aryne, enabling π-extension to afford a larger PAH. This discovery of stannoles as highly reactive - yet stable for handling - diene equivalents, and the development of a modular strategy for their synthesis, should significantly extend the structural scope of PAHs accessible by a [4 + 2] cycloaddition approach.

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