Resolved chiral 3,4-diazaphospholanes and their application to catalytic asymmetric allylic alkylation
Thomas P Clark1, Clark R Landis
1Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, USA.
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 alpha-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.
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