Abstract
5,5′′-dibromo-2,2′:6′,2′′-terpyridine has been synthesized in very good yield and
on a multigram scale modifying the Stille cross-coupling strategy published by Schlüter
and coworkers in a previous work.
Key words
5,5′′-dibromo-2,2′:6′,2′′-terpyridine - Stille cross-coupling - terpyridine derivatives
References
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5-Bromo-2-iodopyridine (5.85 g, 20.5 mmol) was dissolved in 200 mL of toluene. 16.2
mL BuLi (1.4 M in hexane, 22.5 mmol) were added dropwise onto the solution maintained
at -20 °C during the beginning of the addition (after the first drops of BuLi, the
solution became red) and progressively the temperature was lowered to -76 °C. The
solution was then stirred at -76 °C for two hours after which a solution of ClSnMe3 (4.92 g, 24.6 mmol) in toluene was added carefully. At the end of the addition the
yellow solution was stirred for one additional hour at -76 °C and then allowed to
warm up to r.t. Toluene was evaporated and the crude product taken up in CH2 Cl2 . Insoluble salts were filtered off on a sintered glass. The filtrate was evaporated
to dryness and the resulting yellow oil was submitted to a very fast chromatography
(15 min, over 100 g of oven dried alumina,
eluted with ether). This short purification afforded 3 in 97% yield (6.39 g, yellow oil).
1 H NMR (200 MHz, CDCl3 ): δ = 8.82 (d, 1 H, H6 , 4
J = 2.5 Hz); 7.68 (dd, 1 H, H4 , 3
J = 8.1 Hz, 4
J = 2.5 Hz); 7.35 (d, 1 H, H3 , 3
J = 8.1 Hz); 0.32 (s with Sn satellites, 9 H, CH3,
J [1H-119Sn] = 54.4 Hz, J [1H-117Sn] = 51.2 Hz). MS (EI): m/z = 321.0 ([M+ ] calcd 320.8).
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Wang X.
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5-Bromo-2-trimethylstannylpyridine 3 (6.4 g, 19.9 mmol) and 2,6-diiodopyridine 5 (3.17 g, 9.5 mmol) were dissolved in toluene (200 mL). The solution was degassed
three times, Pd(PPh3 )4 (660 mg, 0.6 mmol) added, and the mixture was degassed three times again. The solution
was heated at reflux for 18 h. Pd0 was filtered off and the solvent evaporated. Filtration of the resulting solid on
alumina with CH2 Cl2 as eluent yielded 6 in 90% yield (3.32 g, white solid, according to 1 H NMR, purity is ≥ 95%). All spectroscopic data are in good agreement with literature.
[5 ]