Cross-Coupling Reactions with Acetylenic Dithiafulvenes

Katrine Qvortrup; Asbjørn Sune Andersson; Jan-Philipp Mayer; Anne Sofie Jepsen; Mogens Brøndsted Nielsen

doi:10.1055/s-2004-835641

LETTER

Cross-Coupling Reactions with Acetylenic Dithiafulvenes

Katrine Qvortrup^a,b, Asbjørn Sune Andersson^a, Jan-Philipp Mayer^b, Anne Sofie Jepsen^b, Mogens Brøndsted Nielsen*^a
^a Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark
Fax: +4535320212; e-Mail: mbn@kiku.dk;
^b Department of Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark

Abstract

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Abstract

The scope of acetylenic dithiafulvenes in palladium-catalyzed cross-coupling reactions is reported. From such reactions we have obtained a selection of new extended tetrathiafulvalenes (TTFs), based on p-diethynylbenzene, tri-, and tetraethynylethene cores.

Key words

alkynes - conjugation - cross-coupling - enynes - heterocycles

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References

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Experimental Procedure for Preparation of 8: Compound 1 (418 mg, 1.27 mmol) was desilylated to form 2 as previously described (ref.^1b). To a mixture of CuI (3.5 mg) and Pd(PhCN)₂Cl₂ (20 mg) under argon was added argon-degassed THF (0.5 mL), toluene (0.5 mL), HN(i-Pr)₂ (0.17 mL). Then P(t-Bu)₃ (10% in hexane, 0.125 mL) was added and hereafter dibromide 7 (156 mg, 0.413 mmol), which resulted in a dark brown mixture. This mixture was transferred via a syringe to the flask containing solid 2. The mixture was subjected to ultrasonification at 30 °C for 4 h, whereupon it was filtered through a plug of silica (eluent: CH₂Cl₂). Column chromatography (SiO₂, CH₂Cl₂ → CH₂Cl₂-EtOAc 10:1) afforded 8 as a red-brown solid (253 mg, 84%). Mp 143-146 °C (decomp.). UV/Vis (CHCl₃): λ (ε/M^-1cm^-1): 294 (15200), 333 (15300), 378 (14500), 454 (39000) nm. ¹H NMR (300 MHz, CDCl₃): δ = 0.23 (s, 18 H), 3.83 (s, 6 H), 3.84 (s, 6 H), 5.65 (s, 2 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = -0.2, 53.4 (two overlapping), 92.7, 96.1, 97.4, 101.8, 105.2, 112.5, 118.6, 130.6, 132.2, 148.0, 159.3, 159.7 ppm. MALDI-TOF-MS (matrix: 2,5-dihydroxy-benzoic acid): m/z = 728 [M⁺]. Anal. Calcd for C₃₂H₃₂O₈S₄Si₂ (729.03): C, 52.72; H, 4.42. Found: C, 52.96; H, 4.82.

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