title: Copper(II)- and palladium(II)-catalyzed enantioselective Claisen rearrangement of allyloxy- and propargyloxy-indoles to quaternary oxindoles and spirocyclic lactones.
abstract: In this Article, a strategy to obtain highly enantioselective catalysts for the Claisen rearrangement of allyloxy- and propargyloxy-indoles is outlined. Ultimately, copper BOX and palladium BINAP or PHOX catalysts were discovered as superior in catalyzing Claisen rearrangements of allyloxy- or proparyloxy-substituted indoles to generate oxindoles bearing allyl- or allenyl-substituted quaternary centers. This method proved to be tolerant of a broad range of functional groups. Tandem reactions of the silyl-allene products provide rapid access to a variety of spirocyclic oxindoles in one operation.
authors.affiliation: Department of Chemistry and Penn-Merck High Throughput Experimentation Laboratory, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Trung
authors.initials: T
authors.lastname: Cao
authors.forename: Elizabeth C
authors.initials: EC
authors.lastname: Linton
authors.forename: Joshua
authors.initials: J
authors.lastname: Deitch
authors.forename: Simon
authors.initials: S
authors.lastname: Berritt
authors.forename: Marisa C
authors.initials: MC
authors.lastname: Kozlowski
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry; D000078183:Oxindoles; D010165:Palladium / Q000737:chemistry*; D013141:Spiro Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D007211:Indoles; D007783:Lactones; D058116:Lewis Acids; D000078183:Oxindoles; D013141:Spiro Compounds; C022960:2-oxindole; D010165:Palladium; D003300:Copper