Selective Metalation of 1,3-Dithiole-2-thiones: An Effective Preparation of New Symmetrically and Nonsymmetrically Tetraarylated Tetrathiafulvalenes

Abstract

We report an efficient preparation of fully functionalized tetrathiafulvalene derivatives (TTF) with an extended π-system via a selective magnesiation of 1,3-dithiole-2-thiones (DTT) using 2,2,6,6-tetramethylpiperidin-1-ylmagnesium chloride–lithium chloride (TMPMgCl·LiCl); subsequent reaction with various electrophiles, such as halides, acid chlorides, allyl bromides, and aryl iodides, smoothly led to new mono- and difunctionalized 1,3-dithiole-2-thione derivatives. A triethyl phosphite mediated cross-coupling of the disubstituted 1,3-dithiole-2-thione derivatives with their oxygen analogues gave access to new symmetrically and nonsymmetrically tetraarylated tetrathiafulvalenes of interest as organic materials.

Key words

metalation - organomagnesium reagents - palladium - cross-coupling - organic materials

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