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DOI: 10.1055/s-2004-835641
Cross-Coupling Reactions with Acetylenic Dithiafulvenes
Publikationsverlauf
Publikationsdatum:
08. November 2004 (online)
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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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1a
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References
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8The acetylene and acetylide structures were geometry optimized at the semiempirical PM3 level. Frequencies were calculated to verify that the calculated structures are local minima on the potential energy surface and to correct for zero-point kinetic energies. Single-point energy calculations were performed on the optimized structures at the B3LYP/6-311++G(2d,p) level.
9All new compounds were fully characterized by 1H NMR and 13C NMR spectroscopy, elemental analysis and/or HRMS.
13Experimental 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.