title: Synthesis of the cytotrienin A core via metal catalyzed C-C coupling.
abstract: A synthetic approach to the C17-benzene ansamycins via metal catalyzed C-C coupling is described. Key bond formations include direct iridium catalyzed carbonyl crotylation from the alcohol oxidation level followed by chelation-controlled Sakurai-Seyferth dienylation to form the stereotriad, which is attached to the arene via Suzuki cross-coupling. The diene-containing carboxylic acid is prepared using rhodium catalyzed acetylene-aldehyde reductive C-C coupling mediated by gaseous hydrogen. Finally, ring-closing metathesis delivers the cytotrienin core.
authors.affiliation: University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Rössle
authors.forename: David J
authors.initials: DJ
authors.lastname: Del Valle
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D007495:Iridium / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry; D012294:Rifamycins / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000438:Alcohols; D000447:Aldehydes; D012294:Rifamycins; C106761:cytotrienin A; D007495:Iridium; D012238:Rhodium