title: Deciphering the Origin of Stereoinduction in Cooperative Asymmetric Catalysis Involving Pd(II) and a Chiral Brønsted Acid.
abstract: The density functional (M06) computations on a cooperative multicatalytic reaction involving palladium acetate and a chiral Brønsted acid in the conversion of an indenyl cyclobutanol to spirocyclic indene bearing a quaternary carbon ring junction are reported. A chiral Pd-bis-phosphate is identified as the active catalyst in the enantioselective ring expansion as compared to alternative possibilities wherein the chiral phosphate/phosphoric acid is in the outer sphere of palladium. The enantiocontrolling transition state exhibited more effective C-H···π interactions, lower distortion of the catalyst, and an orthogonal orientation of the bulky phosphate ligands.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
authors.forename: Garima
authors.initials: G
authors.lastname: Jindal
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
authors.forename: Raghavan B
authors.initials: RB
authors.lastname: Sunoj