A novel dry route to ortho-functionalized triarylbismuthanes that are difficult to access by conventional wet routes

Abstract

When an aryl iodide bearing an electron-withdrawing group at the ortho position was milled together with bismuth shots and calcite grains in the presence of Cu powder and CuI using a laboratory ball mill, the corresponding ortho-functionalized triarylbismuthane was obtained in moderate to good yield.

One-Pot Synthesis of Hypervalent Diaryl(iodo)bismuthanes from o-Carbonyl Iodoarenes by Zincation

“…Several mild bismuth-carbon bond forming reactions have been reported, which include the treatment of aryl iodides with bismuth shot in the presence of Cu and CuI by ball milling [17], the arylation of bismuth(III) carboxylates by sodium tetraarylborate [18], and the reaction of BiCl 3 with organozinc reagents [19]. To achieve wide functional group tolerance, we chose organozinc reagents because they are compatible with carbonyl functionalities such as ester, acetyl, and even formyl substituents, and the chemistry of these reagents is well established [20][21][22].…”

Palladium-Catalyzed Cross-Coupling of Arenediazonium Salts with Organoindium or Organobismuth Reagents

“…Tris(3,5-dimethoxyphenyl)bismuthane (7b). 12 Starting from 3,5-dimethoxybromobenzene (1.075 g, 5.00 mmol) compound 7b (354 mg, 0.57 mmol, 57%) was obtained: off-white solid, mp 84 -86 °C; 1 H NMR (400 MHz, CDCl3) δ 6.97 (d, J = 2.2 Hz, 6H), 6.36 (t, J = 2.2 Hz, 3H), 3.71 (s, 18H); 13 Tris(3-methoxyphenyl)bismuthane (7c). 9 Starting from 3-methoxybromobenzene (9.35 g, 6.28 mL, 50.00 mmol) compound 7c (2.89 g, 5.45 mmol, 55%) was obtained: orange-coloured solid, mp 84 -87 °C; 1 H NMR (400 MHz, CDCl3) δ 7.30-7.28 (m, 3H), 7.28-7.24 (m, 6H), 6.79 -6.74 (m, 3H), 3.63 (s, 9H); 13 Tris(2,4-difluorophenyl)bismuthane (7d).…”

“…After filtration diazonium salt 3h (324 mg, 1.30 mmol, 13%) was obtained: yellow solid, mp 130 °C (decomposition). 1 H NMR (400 MHz, DMSO-d6) δ 8.97 (d, J = 2.9 Hz, 1H), 8.05 (dd, J = 10.1, 3.0 Hz, 1H), 6.58 (d, J = 10.2 Hz, 1H); 13 General procedure for the coupling of arene diazonium tetrafluoroborates and aryl indium reagents. Solutions of aryl Grignard reagents were prepared by reacting the respective bromoarene (1.0 equiv.)…”

Organobismuth Reagents: Synthesis, Properties and Applications in Organic Synthesis

“…Functionalized triarylbismuthines bearing electronwithdrawing groups at the ortho position can also be prepared using a ball mill method developed by Suzuki in 2003 (Step 14d). 62 In this procedure, an aryl iodide is milled at room temperature with bismuth shots and calcite grains in the presence of copper powder and copper iodide using a laboratory ball mill. Functional groups such as fluorides, chlorides, bromides, nitro groups, trifluoromethyl, benzylimine and esters are tolerated using this method.…”