(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯和(Z)-2-苯氧(硫)亚甲基-γ-戊内酯的简便合成

A Facile Syntheses of (Z)-2-Phenoxy(THIO)methylene-γ-pentanolide and (Z)-2-Phenoxy(THIO)methyl-2-penten-γ- lactone

以 3 -苯氧 (硫 )基丙炔 ( 1 )为原料 ,经 5步反应合成 ( Z) -2 -苯氧 (硫 )基甲基 -2 -戊烯 -γ-内酯 ( 8)和 ( Z) -2 -苯硫亚甲基 -γ-戊内酯 ( 9) .合成关键步骤为 TMSCl/Na I/H2 O/CH3CN体系中化合物 ( 3 )

Starting from 3 phenoxy(thio) 1 propyne 1a(1b), 5 phenoxy(thio) 3 pentyn 2 ol 2a(2b) were obtained by Grignard reaction. After treating 2a(2b) with Jones reagent, hydroiodination of 3a(3b) with a reagent system of TMSCl/NaI/H 2O in CH 3CN, the conjugated product ( Z ) 5 phenoxy(thio) 4 iodo 3 pentene 2 one 4a(4b) and de conjugated product ( Z ) 5 phenoxy(thio) 4 iodo 3 pentene 2 one 5a(5b) were generated. In the presence of Pd(PPh 3) 4, Et 3N, and CO in toluene, the intramolecular cyclization of reducing products of 4a(4b) and 5a(5b) afforded the target compounds ( Z ) 2 phenoxy(thio) methylene γ pentanolide 9a(9b) and ( Z ) 2 phenoxy(thio) methyl 2 penten γ lactone 8a(8b) respectively in good yields. All compounds have been fully characterized by 1H and 13 C NMR , IR and MS spectroscopy. The one pot deconjugation and hydroiodination of 3a(3b) with a reagent system of TMSCl/NaI/H 2O in CH 3CN was the key step.