ol5b00860_si_001.pdf (3.92 MB)
Deciphering the Origin of Stereoinduction in Cooperative Asymmetric Catalysis Involving Pd(II) and a Chiral Brønsted Acid
journal contribution
posted on 2015-06-19, 00:00 authored by Garima Jindal, Raghavan B. SunojThe
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.
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spirocyclic indeneorthogonal orientationpalladium acetateCooperative Asymmetric Catalysisquaternary carbon ring junctionenantiocontrolling transition stateChiral Br ønsted AcidThe densityphosphate ligandsenantioselective ring expansionindenyl cyclobutanolalternative possibilitieschiral Br ønsted acidmulticatalytic reactioncatalyst
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