Synthesis of Electron-Rich Thiamacrocycles

Abstract

The stepwise syntheses of large [4+4] electron-rich thiamacrocycles, which aim at fullerene complexation, were performed using two types of building blocks, viz. 1,4-bis(bromomethyl)benzene or its dibutoxylated analogue and 4,5-bis(2-cyanoethyl­sulfanyl)-1,3-dithiole-2-thione. Alternatively, a multicomponent mixture of thiamacrocycles, ranging in size from [2+2] to [6+6] units, was generated by the direct reaction of bis(tetraethylammonium) bis(thioxo-1,3-dithiole-4,5-dithiol)zincate with 1,4-bis(bromomethyl)-2,5-dibutoxybenzene, and the individual macrocycles were successfully separated.

Key words

alkylation - arenes - atropoisomerism - macrocycles - thiols

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Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre 12, Union Road, Cambridge, CB2 1EZ, UK under deposition numbers: 6b: CCDC 786385; 8b-anti: CCDC 786386; 8b-syn: CCDC 786387 [fax: [phone], e-mail: [e-mail]].