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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Aromatic Ring-Fused Dipyrrins: Programmed [4 + 2]-Cycloaddition Pathway with Regio-selectivity upon
Jiayang Liu1, Yuanyuan Wang1, Ning Qiu2
1Key Laboratory for Advanced Materials, Shanghai Key Laboratory of Functional Materials Chemistry, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry & Molecular Engineering, East China University of Science & Technology, Shanghai 200237, China.
Abstract:
Sulfolenodipyrrins are employed as building blocks to concisely and efficiently construct aromatic rings (e.g., naphthoquinone, anthraquinone, fullerenes, and phthalimide) from fused dipyrrins by programmed [4 + 2]-cycloaddition reactions. Notably, alkylamino-substitution at the α-position not only enhances the reactivity of sulfolenodipyrrins but also results in the regio-selectivity of the cycloaddition reactions. Theoretical calculations in terms of frontier orbitals of dienes, energy of dienes, steric hindrance, and aromaticity have been conducted to understand the reason in depth. Additionally, the fusion of aromatic groups enables bathochromic absorption with up to ∼130 nm for the monoadducts and to ∼200 nm for the bis-adducts. The phthalimide annulation dipyrrin displays red emission, while the other mono- or bis-adducts do not, owing to the presence of typical acceptors such as quinone analogs or fullerene.
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