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C2-Symmetric Bisphosphinobioxazoline as a Chiral Ligand. Highly Enantioselective Palladium-Catalyzed Allylic Substitutions and Formation of P,N,N,P Tetradentate Palladium (II) Complexes

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journal contribution
posted on 20.05.1999, 00:00 by Sang-gi Lee, Chung Woo Lim, Choong Eui Song, Kwan Mook Kim, Chul Ho Jun
The C2-symmetric bisphosphinobioxazoline [(S,S)-Phos-Biox] 4 was found to be a highly efficient chiral ligand for Pd-catalyzed enantioselective allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate and afforded enantioselectivities of up to 97% ee. Moderate enantioselectivities have been observed in Pd-catalyzed desymmetrizations of cis-1,4-bis(benzoyloxy)cyclopent-2-ene (12) with dimethyl malonate (51−78% yield, 38−58% ee) and N-benzyl-N-methylamine (87% yield, 33% ee) nucleophiles and of biscarbamate 15 of cis-1,4-dihydroxycyclopent-2-ene (90% yield, 50% ee). A 1:1 molar mixture of (S,S)-Phos-Biox 4 with Pd(CH3CN)2Cl2 and [(η3-C3H5)PdCl]2 afforded the P,N,N,P-tetradentate Pd(II) complexes 19a and 19b, respectively. The structures of the complexes 19a,b were determined by X-ray analysis. The complex 19a also exhibited high enantioselectivity (86% yield, 92% ee) in allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate.