Programmed Site-Selective Palladium-Catalyzed Arylation of Thieno[3,2-b]thiophene

T M Ha Vuong; Didier Villemin; Hung-Huy Nguyen; Tin Thanh Le; Tung T Dang; Hien Nguyen

doi:10.1002/asia.201700562

Programmed Site-Selective Palladium-Catalyzed Arylation of Thieno[3,2-b]thiophene

Chem Asian J. 2017 Nov 2;12(21):2819-2826. doi: 10.1002/asia.201700562. Epub 2017 Oct 2.

Authors

T M Ha Vuong^{1

2}, Didier Villemin², Hung-Huy Nguyen³, Tin Thanh Le⁴, Tung T Dang^{1

5}, Hien Nguyen⁶

Affiliations

¹ Faculty of Applied Sciences, Ton Duc Thang University, 19 Nguyen Huu Tho Street, Tan Phong Ward, District 7, Ho Chi Minh City, Vietnam.
² LCMT, UMR 6507, ENSICAEN, Normandie Université France, 6 bd Maréchal Juin, 14000, Caen Cedex, France.
³ Department of Chemistry, VNU-Hanoi University of Science, 19 Le Thanh Tong Street, Ha Noi, Vietnam.
⁴ Faculty of Chemistry, Hochiminh National University of Education, 280 An Duong Vuong, Hochiminh, Vietnam.
⁵ COBRA UMR 6014 Batiment IRCOF, Normandie Université France, 1 Rue Tesniere, 76821, Mont St Aignan Cedex, France.
⁶ Division of Organic Chemistry, Faculty of Chemistry, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Ha Noi, Vietnam.

PMID: 28569412
DOI: 10.1002/asia.201700562

Abstract

Mono-, di-, tri-, and tetraarylated thieno[3,2-b]thiophenes were synthesized by direct site-selective Pd-catalyzed C-H activation reactions with various aryl bromides in the presence of a phosphine-free Pd(OAc)₂ /KOAc catalyst system in N,N-dimethylacetamide (DMAc). The arylation of 2-arylthieno[3,2-b]thiophene took place at the C3 position if the 2-aryl substituents possessed electron-withdrawing groups and at the C5 position if they were bulky and possessed electron-donating groups.

Keywords: C−H activation; metalation; palladium; site selectivity; sulfur heterocycles.