Tetrathiafulvalene‐[2.2]paracyclophanes: Synthesis, crystal structures, and chiroptical properties

Abstract

Two racemic tetrathiafulvalene-[2.2]paracyclophane electron donors EDT-TTF-[2.2]paracyclophane 1 and (COOMe) -TTF-[2.2]paracyclophane 2 have been synthesized via the phosphite mediated cross coupling strategy. Chiral HPLC allowed the optical resolution of the (R ) and (S ) enantiomers for both compounds. Solid-state structures of (R )-1 and (rac)-2 have been determined by single crystal X-ray analysis. Intermolecular π-π and S•••S interactions are disclosed in the packing. Single crystal X-ray analysis of (R )-1 combined with experimental and theoretical circular dichroism spectra allowed the assignment of the absolute configuration of the enantiomers of 1 and 2.

Enantiopure planar chiral [2.2]paracyclophanes: Synthesis and applications in asymmetric organocatalysis

“…Although costly, this approach has been extensively applied in paracyclophane chemistry to access a variety of enantiopure products, such as pCp-based acids (for a selected example, see Lämmehofer et al 25 ), anilines (for a selected example, see Meyer-Eppler et al 26 ), imines or hydrazones (for a selected example, see Masterson et al 27 ), and sulfur-containing compounds (for a selected example, see Deschamps et al 28 ) among many others. [29][30][31][32][33] Moreover, even if it is not always easy to implement, preparative chiral HPLC today remains a method of choice for the late-stage separation of complex pCp molecules (for a selected example, see Hasegawa et al 34 ). Despite earning less recognition as a resolution method in comparison with HPLC, gas chromatography (GC) is a valuable technique frequently employed for separating and analyzing low-molecular-weight organic compounds.…”

Synthesis of 4-(2-Hydroxyaryl)-5-Methyl-1,3-Dithiol-2-Thiones

“…[1][2][3][4] In general, charge-transfer [5][6][7][8][9][10][11][12][13][14][15] or push-pull [16][17][18][19][20] compounds have significant applications in the field of conducting materials. For these reasons heterocyclic compounds -especially those containing sulfur and nitrogen -represent an important resource for the material chemistry [21][22][23][24] and also for medicinal chemistry. [25][26][27][28][29] Important precursors for tetrathiafulvalenes are the 1,3-dithiol-2-thione derivatives.…”

Synthesis of 2-Pyrrolydinyl-1,3-Dithiolium Derivatives from Propiophenones

“…Since the discover y of the metallic conductivity in a tetrathiafulvalene-tetracyanoquinodimethane complex [2] tetrachalcogenafulvalenes have played a leading role in the development of new molecular metals and superconductors [3][4][5]. In general, charge-transfer [6][7][8][9][10][11][12] or push-pull [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] compounds have important applications in the field of conducting materials. For these reasons heterocyclic compounds -especially those containing sulfur and nitrogen -represent an important resource for the material chemistry [30][31][32][33][34][35][36][37][38][39] and not only (biologically active compounds, daily life and even the educational process) [40][41][42][43][44][45][46][47]…”