The "Methyl Effect" in The Enantioselective Allylic Substitution Using Palladium/Chiral Pyridinylmethyl-oxazolines

Chem. J. Chinese Universities ›› 2001, Vol. 22 ›› Issue (12): 2032.

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The "Methyl Effect" in The Enantioselective Allylic Substitution Using Palladium/Chiral Pyridinylmethyl-oxazolines

LI ZhiPeng¹, TANG FangYi¹, WU XinYan¹, ZHOU QiLin^1,2, Albert S. C. Chan³

1. Instituteof Fine Chemicals, East China University of Scienceand Technology, Shanghai 200237, China;
2. State Key Laboratoryand Institute of Elemento-Organic Chemistry, NankaiUniversity, Tianjin 300071, China;
3. Department of Applied Biology & Chemical Technology, the Hong Kong Polytechnic University, Hong Kong, China

Received:2001-04-29 Online:2001-12-24 Published:2001-12-24

Abstract

Abstract: In this paper, two types of chiral ligands 1 and 2 containing pyridinyl moiety and oxazolines bridged by a methylene group were investigated in the palladium catalyzed substitution of 1,3 diphenyl 2 propenyl acetate with dimethyl malonate. Ligands 2, which have two methyl groups at the bridged methylene, gave higher enantioselectivities than their unsubstituted analogues 1. This "methyl effect" increased while the substituent on the C₄ in the oxazoline ring was changed from benzyl to tert butyl. Despite of that the "methyl effect" was found in the palladium catalyzed enantioselective allylic substitution, it was obviously significant for assisting rational design of chiral ligands and catalysts in other asymmetric reaction.

Key words: Asymmetric catalysis, Allylic substitution, Chiral pyridinyl oxazoline ligand

CLC Number:

O625

TrendMD:

LI ZhiPeng, TANG FangYi, WU XinYan, ZHOU QiLin, Albert S. C. Chan . The "Methyl Effect" in The Enantioselective Allylic Substitution Using Palladium/Chiral Pyridinylmethyl-oxazolines[J]. Chem. J. Chinese Universities, 2001, 22(12): 2032.

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The "Methyl Effect" in The Enantioselective Allylic Substitution Using Palladium/Chiral Pyridinylmethyl-oxazolines

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