Bi-2-naphthol(BINOL) enantiomers were baseline resolved on HPLC network-polymeric chiral stationary phase (Kromasil CHI-DMB, based on O,O′-di(3,5-dimethylbenzoyl)N,N′-diallyl-L-tartaric diamide). The effects of the ...Bi-2-naphthol(BINOL) enantiomers were baseline resolved on HPLC network-polymeric chiral stationary phase (Kromasil CHI-DMB, based on O,O′-di(3,5-dimethylbenzoyl)N,N′-diallyl-L-tartaric diamide). The effects of the column temperature, the type and the concentration of the polar alcohol modifier in the binary mobile phase on the chiral resolution were examined. The separation value was 1.191 when V(hexane)∶V(2-propanol)=95∶5 was used as mobile phase at a flow rate of 1.0 mL/min at 25 ℃ with retention time being within 14 minutes. The mechanism of the chiral recognition was discussed with the calculated thermodynamic parameters. It is suggested that hydrogen bonding interaction between hydroxyl group of the solute and the CSP play important roles in chiral recognition. The chiral resolution is enthalpy-entropy driven and the enthalpy contribution is greater. 1,1′-Bi-2-naphthyl di-p-toluenesulfonate, 1,1′-bi-2-naphthyl diacetate and 1,1′-bi-2-naphthyl dicinnamate could not be resolved at experiment conditions used.展开更多
A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with...A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with n butyl lithium. Mandelonitrile was prepared in an isolated yield 70% with more than \{e.e.\} =60%. The effect of solvents and the amount of catalyst on enantioselectivity was also investigated.展开更多
Experimental results are reported for the CuCl2-mediated asymmetric oxidative coupling of 2-naphthols in the presence of [-]α-methylbenzylamine to optically active （S）-（-）-1,1-bi-2-naphthol. Under anhydrous con...Experimental results are reported for the CuCl2-mediated asymmetric oxidative coupling of 2-naphthols in the presence of [-]α-methylbenzylamine to optically active （S）-（-）-1,1-bi-2-naphthol. Under anhydrous conditions and with a 3∶1 molarity ratio of α-methylbenzylamine to 2-naphthol, a fair enantioselection has been observed（up to 80.6% ee）.展开更多
A new polymer supported BINOL ligand(4) was prepared by means of anchoring binaphthyl molecule(3) to aminoethylated polystyrene through a procedure of solid phase peptide synthesis. The key compound ( R ) 2,2 dihydr...A new polymer supported BINOL ligand(4) was prepared by means of anchoring binaphthyl molecule(3) to aminoethylated polystyrene through a procedure of solid phase peptide synthesis. The key compound ( R ) 2,2 dihydroxy 1,1 binaphthyl 3 carboxylic acid(3) was prepared from R BINOL by protection of hydroxyl groups and then reaction with n butyllithium followed by carboxylation. By controlling the amount of BuLi, (3) was obtained in 55% overall yield. Ligand (4) was prepared through condensation of (3) with aminoethylated polystyrene in the presence of DCC and HOBt and found to have a loading of 0.40 mmol/g (by mass increase). The linkage between binaphthyl and aminoethylated polystyrene was indicated by a new absorption in IR spectrum of (4) at 1 644 cm -1 in comparing with what of the polystyrene. By mixing (4) with Ti(OiPr) 4 in dry CH 2Cl 2, a complex was easily prepared and this complex was found to be an efficient heterogeneous catalyst in asymmetric addition of diethylzinc to aldehydes. Optical active alcohols with up to 82% ee were obtained from the asymmtric addition with high chemical yields when 20% of (4) was used. And when benzaldehyde was used as substrate, we found that enantioselectivity increased obviously when the amount of (4) used in reaction increased from 5% to 20%;decreased the load of BINOL in ligand (4) reduced the ee of addition product; and R form of products was resulted. [WT5HZ]展开更多
文摘Bi-2-naphthol(BINOL) enantiomers were baseline resolved on HPLC network-polymeric chiral stationary phase (Kromasil CHI-DMB, based on O,O′-di(3,5-dimethylbenzoyl)N,N′-diallyl-L-tartaric diamide). The effects of the column temperature, the type and the concentration of the polar alcohol modifier in the binary mobile phase on the chiral resolution were examined. The separation value was 1.191 when V(hexane)∶V(2-propanol)=95∶5 was used as mobile phase at a flow rate of 1.0 mL/min at 25 ℃ with retention time being within 14 minutes. The mechanism of the chiral recognition was discussed with the calculated thermodynamic parameters. It is suggested that hydrogen bonding interaction between hydroxyl group of the solute and the CSP play important roles in chiral recognition. The chiral resolution is enthalpy-entropy driven and the enthalpy contribution is greater. 1,1′-Bi-2-naphthyl di-p-toluenesulfonate, 1,1′-bi-2-naphthyl diacetate and 1,1′-bi-2-naphthyl dicinnamate could not be resolved at experiment conditions used.
文摘A series of aromatic cyanohydrins and their O silyl ethers have been synthesized by trimethylsilylcyanation of aromatic aldehydes using a catalyst generated in situ from optically active R (+) 1,1 2 bisnaphthol with n butyl lithium. Mandelonitrile was prepared in an isolated yield 70% with more than \{e.e.\} =60%. The effect of solvents and the amount of catalyst on enantioselectivity was also investigated.
文摘Experimental results are reported for the CuCl2-mediated asymmetric oxidative coupling of 2-naphthols in the presence of [-]α-methylbenzylamine to optically active （S）-（-）-1,1-bi-2-naphthol. Under anhydrous conditions and with a 3∶1 molarity ratio of α-methylbenzylamine to 2-naphthol, a fair enantioselection has been observed（up to 80.6% ee）.
文摘A new polymer supported BINOL ligand(4) was prepared by means of anchoring binaphthyl molecule(3) to aminoethylated polystyrene through a procedure of solid phase peptide synthesis. The key compound ( R ) 2,2 dihydroxy 1,1 binaphthyl 3 carboxylic acid(3) was prepared from R BINOL by protection of hydroxyl groups and then reaction with n butyllithium followed by carboxylation. By controlling the amount of BuLi, (3) was obtained in 55% overall yield. Ligand (4) was prepared through condensation of (3) with aminoethylated polystyrene in the presence of DCC and HOBt and found to have a loading of 0.40 mmol/g (by mass increase). The linkage between binaphthyl and aminoethylated polystyrene was indicated by a new absorption in IR spectrum of (4) at 1 644 cm -1 in comparing with what of the polystyrene. By mixing (4) with Ti(OiPr) 4 in dry CH 2Cl 2, a complex was easily prepared and this complex was found to be an efficient heterogeneous catalyst in asymmetric addition of diethylzinc to aldehydes. Optical active alcohols with up to 82% ee were obtained from the asymmtric addition with high chemical yields when 20% of (4) was used. And when benzaldehyde was used as substrate, we found that enantioselectivity increased obviously when the amount of (4) used in reaction increased from 5% to 20%;decreased the load of BINOL in ligand (4) reduced the ee of addition product; and R form of products was resulted. [WT5HZ]
