New dihydroxy bis(oxazoline) ligands for the palladium-catalyzed asymmetric allylic alkylation:: Experimental investigations of the origin of the reversal of the enantioselectivity

被引:51
作者
Aït-Haddou, H
Hoarau, O
Cramailére, D
Pezet, F
Daran, JC
Balavoine, GGA
机构
[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
[2] Zyvex Corp, Richardson, TX 75081 USA
[3] CNRS, Chim Coordinat Lab, UPR 8241, F-31077 Toulouse 4, France
关键词
allylic alkylation; asymmetric catalysis; enantioselectivity; N ligands; palladium;
D O I
10.1002/chem.200204649
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The origin of the reversal of the enantioselectivity in the palladium-catalyzed allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate anion using chiral dihydroxy bis(oxazoline) "BO" ligands derived from (1S,2S)-(+)-2-amino-1-phenyl-1,3-propanediol was investigated. To determine the structural effects of the dihydroxy BO ligand on this unique phenomenon, new homochiral dihydroxy BO ligands were prepared from L-threonine and L-serine and were assessed in the transformation. The results obtained with these novel BO ligands, compared with the one obtained by using the dihydroxy BO ligands derived from (1S,2S)-(+)-2- amino-1-phenyl-1,3-propanediol, reveal that the reversal in the enantioselectivity observed with the dihydroxy BO ligand depends on the structure of the ligand. The effect of different bases used to generate the dimethyl malonate anion was also examined. The results are discussed in terms of the interaction of one hydroxy group in the intermediate pi-allyl palladium complex with the dimethyl malonate anion.
引用
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页码:699 / 707
页数:9
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