Resolved Chiral 3,4-Diazaphospholanes and Their Application to Catalytic Asymmetric Allylic Alkylation
- 3 September 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (39) , 11792-11793
- https://doi.org/10.1021/ja036359f
Abstract
One-pot condensation of PhPH2, phthaloyl chloride, and the azine of 2-carboxybenzaldehyde (1) results in the new phosphine, rac-N,N‘-phthaloyl-2,3-(2-carboxyphenyl)-phenyl-3,4-diazaphospholane (rac-2), in 88% yield. Resolution via selective crystallization of the diastereomeric α-methylbenzylamine salts followed by coupling with amino acids and other amines provides rapid access to new collections of chiral phosphines (3). Pd-catalyzed alkylation of 1,3-dimethylallyl acetate and 1,3-diphenylallyl acetate at room temperature in the presence of 3 exhibits enantioselectivities as high as 92% ee and 97% ee, respectively, with strong sensitivity to the nature of the amino acid appendages. The presence of PF6- salts profoundly affects both the yield and the selectivity of catalytic allylic alkylation.Keywords
This publication has 13 references indexed in Scilit:
- Identification of Suitable Ligands for a Transition Metal-Catalyzed Reaction: Screening of a Modular Ligand Library in the Enantioselective Hydroboration of StyreneAdvanced Synthesis & Catalysis, 2002
- Pd Asymmetric Allylic Alkylation (AAA). A Powerful Synthetic Tool.CHEMICAL & PHARMACEUTICAL BULLETIN, 2002
- Mechanism of Enantioselective Ti-Catalyzed Strecker Reaction: Peptide-Based Metal Complexes as Bifunctional CatalystsJournal of the American Chemical Society, 2001
- Rapid Access to Diverse Arrays of Chiral 3,4-DiazaphospholanesAngewandte Chemie International Edition in English, 2001
- Catalytic Asymmetric Allylic Alkylation in Water with a Recyclable Amphiphilic Resin-Supported P,N-Chelating Palladium ComplexJournal of the American Chemical Society, 2001
- Steric and Electronic Ligand Perturbations in Catalysis: Asymmetric Allylic Substitution Reactions UsingC2-Symmetrical Phosphorus-Chiral (Bi)ferrocenyl DonorsThe Journal of Organic Chemistry, 2001
- Asymmetric Catalysis with Libraries of Palladium β-Turn Phosphine ComplexesJournal of the American Chemical Society, 2000
- Platinum-Catalysed Allylic Alkylation: Reactivity, Enantioselectivity, and RegioselectivityChemistry – A European Journal, 2000
- Versatile Ligands for Palladium-Catalyzed Asymmetric Allylic AlkylationAngewandte Chemie International Edition in English, 1998
- Endohedral complexes of fullerene radical cationsJournal of the American Chemical Society, 1991