American Chemical Society
jo0257849_si_001.pdf (9.28 MB)
Download file

Synthesis of Polysubstituted Benzothiophenes and Sulfur-Containing Polycyclic Aromatic Compounds via Samarium Diiodide Promoted Three-Component Coupling Reactions of Thiophene-2-carboxylate

Download (9.28 MB)
journal contribution
posted on 2002-06-12, 00:00 authored by Shyh-Ming Yang, Jiun-Jie Shie, Jim-Min Fang, Sandip Kumar Nandy, Hung-Yu Chang, Syn-Hung Lu, Gladys Wang
By the promotion of samarium diiodide, thiophene-2-carboxylate reacted with 2 equiv of ketones at the C-4 and C-5 positions to give diols such as 2 and 9. Because the intermediary organosamarium species were oxophilic but not too basic, the double hydroxyalkylations with various ketone substrates, including alkyl aryl ketones, acetylthiophenes, cyclohexanone, α-tetralone, and α-phenylacetophenones, were realized without complication of side reactions. The diol products underwent an acid-catalyzed dehydration to give dienes such as 3 and 10, which were treated with DDQ to give either polysubstituted thiophenes (e.g., 4 and 11) or benzothiophenes (e.g., 5, 13, and 14) depending on the reaction conditions. Oxidative annulations of 4,5-diarylthiophenes 11 and 4,5,6,7-tetraphenylbenzothiophenes 14 were carried out by photochemical or chemical methods to give the sulfur-containing polycyclic aromatic compounds, such as phenanthro[9,10-b]thiophene-2-carboxylate, piceno[13,14-b]thiophene-2-carboxylate, and tribenzo[fg,ij,rst]pentapheno[15,16-b]thiophene-2-carboxylates. This method is applicable to the preparation of polysubstituted thiophenes, benzothiophenes, and the related compounds possessing liquid crystalline, photochromic, and other functional properties.