Tertiary amine functionalized polyacrylonitrile fiber catalyst for the synthesis of tetrahydrothiophenes

A tertiary amine immobilized fiber was prepared and used to efficiently catalyze tandem Michael-intramolecular Henry reactions between 1,4-dithiane-2,5-diol and trans-beta-nitrostyrenes to form the corresponding tetrahydrothiophene derivatives. This newly developed fiber catalyst is applicable to a wide range of trans-beta-nitroalkenes and affords good to excellent yields (75-93%) under mild conditions (with 2.5 mol % fiber catalyst at 50 C in ethanol for 5 h). The fiber catalyst exhibits excellent recyclability and reusability (up to 10 times) after simple workup procedure with only a slight loss in catalytic activity. It is noteworthy that the major diastereomers have r-R, trans-nitro, trans-hydroxy configurations with diastereoselectivities of up to 15:1. This differs from the results obtained when the same reaction is catalyzed by a homogeneous catalyst. This is the first example of a fiber catalyst exhibiting excellent diastereoselectivity. (C) 2013 Elsevier Ltd. All rights reserved.