NG Teng Wei and ONG Jun Yang rejoined us as PhD students.

N2 - A regioselective phosphorylation method for myo-inositol was developed by utilizing readily preparable BINOL-derived phosphoramidites. The method also facilitated the complete separation of the diastereomeric products by simple chromatography. Based on this phosphorylation and Ni-catalyzed alkyl-alkyl cross-coupling reaction for long fatty acids, we achieved the first synthesis of a lysophosphatidylinositol, EhPIa having long fatty acid C30:1, as a partial structure of glycosylphosphatidylinositol (GPI) anchor from the cell membrane of a protozoa, Entamoeba histolytica.

Dr. FENG Wei left us to join Sun Yat-sen University, China. Farewell and good luck Wei!

Recently, we were interested in examining the use of H8-BINOL and H4-BINOL in an asymmetric vinylogous Mukaiyama aldol reaction catalyzed by BINOL/Ti(OiPr)4(BITIP). While H8-BINOL is commercially available, to our knowledge, H4-BINOL is not. Moreover, the only published method for the preparation of H4-BINOL involves heating a mixture of Ni/Al alloy, NaOH, H2O, iPrOH and MOM2-BINOL to 80 °C for 24 h at a concentration of 3 μmol/L (ca. 1L of solvent for 1g of substrate) followed by protective group removal, including chromatographic purification following each operation. The prospect of using the above process for a gram to multigram scale synthesis of H4-BINOL 3 led us to examine the development of an alternative procedure.


Dr. Song Xiaoxiao joined the group.

Dr. MA Chao left us for a faculty position in Hubei Univesity, China. Farewell and good luck Chao!

H8-BINOL 3 has been accessed from BINOL 1 using several different hydrogenation conditions;, among these, a straightforward procedure appeared to be the partial hydrogenation of either BINOL enantiomer 1 using Adam’s catalyst (PtO2·(H2O)x) in AcOH, under three atmospheres of H2, which provides enantiomerically pure H8-BINOL.


Dr. MA Chao and HO Yee Ann joined the group.

A regioselective phosphorylation method for myo-inositol was developed by utilizing readily preparable BINOL-derived phosphoramidites. The method also facilitated the complete separation of the diastereomeric products by simple chromatography. Based on this phosphorylation and Ni-catalyzed alkyl-alkyl cross-coupling reaction for long fatty acids, we achieved the first synthesis of a lysophosphatidylinositol, EhPIa having long fatty acid C30:1, as a partial structure of glycosylphosphatidylinositol (GPI) anchor from the cell membrane of a protozoa, Entamoeba histolytica.

YANG Licheng was enrolled for his PhD studies.

Both the H4-BINOL 2 and H8-BINOL 3 ligands have been shown to work well in a number of catalytic asymmetric reactions including the addition of alkylzinc and alkylaluminum reagents to aldehydes and the Hetero-Diels-Alder addition using Danishefsky’s diene. In addition, the enantioselectivities obtained with these ligands surpassed those observed for reactions using the parent BINOL 1 as a ligand.

Dr. Monissa PADERES joined the group.

The chemical synthesis of glycosyl inositol phospholipids from Entamoeba histolytica is reported. The key feature of this synthesis is a regioselective phosphorylation reaction that occurs through desymmetrization of a myo-inositol derivative with phosphoroselenoyl chloride. A new protecting-group strategy was developed that utilizes allyl and alloc groups to synthesize complex glycolipids bearing unsaturated lipids. These developments provided an efficient synthetic route for various complex inositol phospholipids and their analogues. Furthermore, the binding affinity of the synthetic inositol phospholipids with mouse CD1d molecules has been evaluated, as well as the immunostimulatory activity.

RONG Ziqiang was enrolled as PhD student.

A series of 3,3′-disubstituted and 6,6′-disubstituted BINOL derivatives was synthesized and examined in typical titanium(IV) promoted aldol reactions. The model reaction of S-ketene silyl acetal 13 and aldehydes 12a and 12b revealed that 6,6′-dibromo-BINOL derivative (R)-6 is the ligand of choice for these transformations. Up to 97% yield with excellent enantioselectivity (ee > 97%) could be achieved. Scope and limitations were demonstrated using a series of aldehydes as substrates, which were generally transformed into their aldol adducts by the (R)-6/Ti(Oi-Pr)4 catalyst with good efficacy and high enantioselectivity.