Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

Chem. J. Chinese Universities ›› 2003, Vol. 24 ›› Issue (2): 274.

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Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

FAN Qing-Hua¹, YANG Xi-Qiang¹, LIU Guo-Hua¹, CHEN Xiao-Min¹, Albert S. C. Chan²

1. Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China;
2. Open Laboratory of Chirotechnology and Department of Applied Biology and Chemical Technology, Hong Kong, China

Received:2001-12-03 Online:2003-02-24 Published:2003-02-24

Abstract

Abstract: The series of new dendritic chiral BINOL ligands(3) were synthesized by condensation reaction of (R)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid(1) and Fréchet-type poly(aryl ether) dendrons(2) with an amino group at the focal point in moderate reaction yields. All ligands were characterized by ¹HNMR, IR and MALDI-TOF-MS spectra, which clearly demonstrated the formation of monodispersed dendritic BINOLs. The titanium complexes of these dendritic ligands obtained by mixing(3) with Ti(OPrⁱ)₄ 4 in dry toluene were found to be efficient catalysts in asymmetric addition of diethylzinc to aldehydes. The size of the dendritic wedges did not significantly influence the enantioselectivity of the catalyst. Most interestingly, when ortho-chlorobenzaldehyde was used as substrate, we found that enantioselectivity increased slightly with increasing generation of the dendrimers.

Key words: 1,1′-BINOL, Chiral dendrimer, Asymmetric catalysis

CLC Number:

O625.23

TrendMD:

FAN Qing-Hua, YANG Xi-Qiang, LIU Guo-Hua, CHEN Xiao-Min, Albert S. C. Chan . Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes[J]. Chem. J. Chinese Universities, 2003, 24(2): 274.

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Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

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