title: Total synthesis of (+)-trienomycins A and F via C-C bond-forming hydrogenation and transfer hydrogenation.
abstract: The triene-containing C17-benzene ansamycins trienomycins A and F were prepared in 16 steps (longest linear sequence, LLS) and 28 total steps. The C11-C13 stereotriad was generated via enantioselective Ru-catalyzed alcohol CH syn crotylation followed by chelation-controlled carbonyl dienylation. Enantioselective Rh-catalyzed acetylene-aldehyde reductive coupling mediated by gaseous H2 was used to form a diene that ultimately was subjected to diene-diene ring closing metathesis to form the macrocycle. The present approach is 14 steps shorter (LLS) than the prior syntheses of trienomycins A and F, and 8 steps shorter than any prior synthesis of a triene-containing C17-benzene ansamycin.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: David J
authors.initials: DJ
authors.lastname: Del Valle
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000409:Alanine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D006865:Hydrogenation; D047029:Lactams, Macrocyclic / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D047029:Lactams, Macrocyclic; D002244:Carbon; C045958:trienomycin A; D000409:Alanine