Synthesis 2016; 48(01): 103-114
DOI: 10.1055/s-0035-1560728
paper
© Georg Thieme Verlag Stuttgart · New York

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

Julia Nafe
Department of Chemistry, Ludwig-Maximilians-Universität, Butenandtstrasse 5-13, 81377 München, Germany   Email: paul.knochel@cup.uni-muenchen.de
,
Paul Knochel*
Department of Chemistry, Ludwig-Maximilians-Universität, Butenandtstrasse 5-13, 81377 München, Germany   Email: paul.knochel@cup.uni-muenchen.de
› Author Affiliations
Further Information

Publication History

Received: 17 September 2015

Accepted after revision: 22 September 2015

Publication Date:
21 October 2015 (online)


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.

Supporting Information

 
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