title: Access to Spirocyclized Oxindoles and Indolenines via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates with 2-Oxotryptamines and Tryptamines.
abstract: Reported here are methods for the direct construction of a range of spirocyclized oxindoles and indolenines in good to excellent yields. Specifically, we report the palladium-catalyzed reactions of oxindoles and indoles, both functioning as bis-nucleophiles, with propargyl carbonates to afford spirocyclic products having an exocyclic double bond on the newly formed ring. The reaction proceeds through a process wherein the first nucleophilic unit on the oxindole or indole reacts with an allenyl-palladium species, formed from oxidative addition of Pd(0) to propargyl carbonates, to generate a π-allyl palladium intermediate that then reacts further with the second nucleophilic component of the oxindole or indole. The cascade process forges two bonds en route to spirocyclized oxindole and indolenine products. The use of chiral phosphines renders the cyclization sequence enantioselective, providing spirocyclic products with modest to good enantioselectivities.
authors: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
authors: Antoinette E
authors: AE
authors: Nibbs
authors: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
authors: Thomas D
authors: TD
authors: Montgomery
authors: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
authors: Ye
authors: Y
authors: Zhu
authors: Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
authors: Viresh H
authors: VH
authors: Rawal
mesh_terms: D002384:Catalysis; D003500:Cyclization; D007211:Indoles / Q000737:chemistry*; D015394:Molecular Structure; D000078183:Oxindoles; D010165:Palladium / Q000737:chemistry*; D010293:Pargyline / Q000031:analogs & derivatives* / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D014363:Tryptamines / Q000737:chemistry*
chemical_list: D007211:Indoles; D000078183:Oxindoles; D013141:Spiro Compounds; D014363:Tryptamines; C022960:2-oxindole; D010165:Palladium; D010293:Pargyline