Annulation Cascade of Arylnitriles with Alkynes to Stable Delocalized PAH Carbocations Intramolecular Rhodium Migration

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Jul 17

PMID 30009016

Citations 4

Authors

Jiangliang Yin

Fulin Zhou

Lei Zhu

Mufan Yang

Yu Lan

Jingsong You

Affiliations

Soon will be listed here.

Abstract

Herein, we propose the conception of heteroatom-promoted delocalization of the positive charge of an oxonium ion and thus develop a highly efficient rhodium(iii)-catalyzed hydration and three fold C-H activation/annulation cascade of arylnitriles with alkynes, affording a structurally diverse family of delocalized polycyclic aromatic hydrocarbon (PAH) carbocations. DFT calculations demonstrate that the positive charge mostly locates around the C1 atom and is partly delocalized by ambient N, O1 and C5 atoms. A mechanistic study indicates that the hydration of the arylnitrile and three fold insertion of the alkyne is a successive process rather than a step by step process, wherein a unique intramolecular rhodium migration is probably involved. These novel carbeniums show tunable fluorescence emission, low cytotoxicity and the ability to specifically target lysosomes.

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