title: Chemoselective and enantioselective oxidation of indoles employing aspartyl peptide catalysts.
abstract: Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into several classes of alkaloid natural products. Despite this potentially high utility in the total synthesis, reports of catalytic enantioselective indole oxidation remain sparse. Here we report a highly chemoselective catalytic system for the indole oxidation that delivers 3-hydroxy-indolenines with good chemical yields and moderate to high levels of enantio- and diastereoselectivity (up to 95:5 er and up to 92:8 dr). These results represent, to our knowledge, the most selective values yet reported in the literature for catalytic asymmetric indole oxidation. Furthermore, the utility of enantioenriched hydroxy-indolenines in stereospecific rearrangements is demonstrated.
authors.affiliation: Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
authors.forename: Filip
authors.initials: F
authors.lastname: Kolundzic
authors.forename: Mohammad N
authors.initials: MN
authors.lastname: Noshi
authors.forename: Meiliana
authors.initials: M
authors.lastname: Tjandra
authors.forename: Mohammad
authors.initials: M
authors.lastname: Movassaghi
authors.forename: Scott J
authors.initials: SJ
authors.lastname: Miller
mesh_terms: D001224:Aspartic Acid / Q000737:chemistry*; D002384:Catalysis; D007211:Indoles / Q000737:chemistry*; D010084:Oxidation-Reduction; D010455:Peptides / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D007211:Indoles; D010455:Peptides; D001224:Aspartic Acid