Copper-facilitated Suzuki-Miyaura coupling for the preparation of 1,3-dioxolane-protected 5-arylthiophene-2-carboxaldehydes

• Published in: Tetrahedron Vol. 74; no. 16; pp. 2002 - 2008
• Main Authors: Hergert, Tamás, Varga, Bálint, Thurner, Angelika, Faigl, Ferenc, Mátravölgyi, Béla
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 19.04.2018; Elsevier
• Subjects: 5-Formyl-2-thiopheneboronic acid; Anchoring group precursor; Chemistry; Chemistry, Organic; Copper co-catalysis; Dye-sensitized solar cells; Physical Sciences; Science & Technology; Suzuki-Miyaura coupling; Anchoring group precursor; Copper co-catalysis; Dye-sensitized solar cells; Suzuki-Miyaura coupling; 5-Formyl-2-thiopheneboronic acid; SENSITIZED SOLAR-CELLS; REAGENTS; ORGANIC SENSITIZERS; ENERGY-LEVELS; UNITS; STILLE REACTION
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2018.03.001

5-Formyl-2-thiopheneboronic acid is a widely used building block for the synthesis of diverse structures, however, due to a significant instability its transformation to 5-arylthiophene-2-carboxaldehydes by CC couplings could be performed only in low yields. Herein, as a solution, a convenient technique is described for the preparation of 1,3-dioxolane-protected 5-arylthiophene-2-carboxaldehydes via a one-pot borylation–copper(I) chloride co-catalyzed Suzuki-Miyaura coupling reaction. The utilization of the in situ prepared 2-thiopheneboronic ester derivative is allowed by the method developed. Elimination of the crucial, acidic liberation step of boronic acid species resulted in improved yields and purities. In addition, comparison of various aryl bromides is shown to demonstrate the high tolerance of the transformation to functional groups. [Display omitted]