The biomimetic synthesis of SNF4435C and SNF4435D, and the total synthesis of the polyene metabolites aureothin, N-acetyl-aureothamine and spectinabilin

摘要

Full details of the biomimetic conversion of polyene metabolite spectinabilin (5) into the isomeric natural products SNF4435C (1) and SNF4435D (2) by a cascade of E/Z-isomerizations and electrocyclizations are reported. Additionally, short total syntheses of the related natural product, (+/-)-aureothin (3), (+/-)-N-acetyl-aureothamine (4) and (+/-)-spectinabilin (5) are presented. The key steps in the synthesis of (+/-)-3, (+/-)-4 and (+/-)-5 are the construction of the tetrahydrofuran motif using a palladium-catalyzed cycloaddition and the ruthenium-catalyzed cross metathesis of alkene 17 to form the common intermediate, boronic ester 24, which was further transformed using a trans-selective Suzuki coupling with a dibromide and a stereospecific Negishi-type methylation. (c) 2005 Elsevier Ltd. All rights reserved.