title: Enantioselective total syntheses of (-)-palau'amine, (-)-axinellamines, and (-)-massadines.
abstract: Dimeric pyrrole-imidazole alkaloids represent a rich and topologically unique class of marine natural products. This full account will follow the progression of efforts that culminated in the enantioselective total syntheses of the most structurally ornate members of this family: the axinellamines, the massadines, and palau'amine. A bio-inspired approach capitalizing on the pseudo-symmetry of the members of this class is recounted, delivering a deschloro derivative of the natural product core. Next, the enantioselective synthesis of the chlorocyclopentane core featuring a scalable, catalytic, enantioselective Diels-Alder reaction of a 1-siloxydiene is outlined in detail. Finally, the successful divergent conversion of this core to each of the aforementioned natural products, and the ensuing methodological developments, are described.
authors.affiliation: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
authors.forename: Ian B
authors.initials: IB
authors.lastname: Seiple
authors.forename: Shun
authors.initials: S
authors.lastname: Su
authors.forename: Ian S
authors.initials: IS
authors.lastname: Young
authors.forename: Akifumi
authors.initials: A
authors.lastname: Nakamura
authors.forename: Junichiro
authors.initials: J
authors.lastname: Yamaguchi
authors.forename: Lars
authors.initials: L
authors.lastname: Jørgensen
authors.forename: Rodrigo A
authors.initials: RA
authors.lastname: Rodriguez
authors.forename: Daniel P
authors.initials: DP
authors.lastname: O'Malley
authors.forename: Tanja
authors.initials: T
authors.lastname: Gaich
authors.forename: Matthias
authors.initials: M
authors.lastname: Köck
authors.forename: Phil S
authors.initials: PS
authors.lastname: Baran
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis*; D060326:Chemistry Techniques, Synthetic; D006146:Guanidines / Q000138:chemical synthesis*; D007093:Imidazoles / Q000138:chemical synthesis*; D011758:Pyrroles / Q000138:chemical synthesis*; D013141:Spiro Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D006146:Guanidines; D007093:Imidazoles; D011758:Pyrroles; D013141:Spiro Compounds; C520388:axinellamine; C478874:massadine; C438976:palau'amine