A concise, versatile, and catalytic enantioselective approach to natural and non-natural isopavine alkaloids has been developed. The synthesis takes advantage of catalytic asymmetric reaction to construct the pivotal stereogenic center in a highly enantioselective way (95–98% ee), and features use of intramolecular Pictet–Spengler reaction to build the core tetracyclic skeleton in a rapid and stereoselective fashion.

A series of ferrocene-based bifunctional phosphinothiourea organocatalysts were synthesized and applied to the enantioselective Morita–Baylis–Hillman reaction of acrylates with nitrobenzaldehydes, giving the desired products in up to 99.7 % ee. The strong electron-withdrawing effect of nitro group and hydrogen bonding interactions between the thiourea moiety of catalyst and aldehyde might be crucial during the enantio-controlling process.

A new type of ferrocene-based phosphine-tert-butylsulfinamide ligand has been synthesized and applied to the enantioselective formation of C–C and C–N bonds. The palladium complex derived from ligand 4a was an efficient catalyst in asymmetric allylic substitution of several substrate types. Enantioselectivites with the difficult substrate 3-acetoxycyclohexene of up to 91% ee are achieved.

Prostate cancer cells can switch from an androgen-dependent state to an androgen-independent state after a continuous androgen ablation therapy. However, the molecular mechanisms underlying this switch are still unclear. Therefore, we explored the change in androgen receptor (AR)-related gene expression during this transition in a novel cell model.Prostate cancer cells were continuously treated with competitive androgen receptor inhibitor hydroxyflutamide for 1.5 years, which yielded an flutamide-insensitive LNCaP subline, LNCaP-flu, as confirmed by MTT assays, flow cytometry, and electron microscopy. We analyzed the differences in gene expression in LNCaP-flu cells and LNCaP cells using gene chips and follow-up RT-PCR.Over 2,428 genes were differentially expressed between these cell lines: 1,194 were down-regulated and 1,234 were up-regulated. Three genes in particular were considered related to the androgen-dependent transition: NCOR1, TIF2 (NCOA2), and ARA70 (NCOA4). There were no apparent changes in expression of the androgen receptor or prostate-specific antigen.ARs and associated coregulators play a central role in the flutamide-insensitive transition of prostate cancer cells. Although AR expression does not change during this transition, the change in AR coregulators may be a critical factor in the development of antiandrogen insensitivity

The highly enantioselective synthesis of (R)-isopropyl 3-(3′,4′-dihydroxyphenyl)-2-hydroxypropanoate and its enantiomer has been achieved starting from 3,4-dihydroxybenzaldehyde. The stereogenic centers were established through asymmetric dihydroxylation of (E)-isopropyl 3,4-bis(benzyloxy) cinnamate. A convenient manipulation in selective catalytic hydrogenation and deprotection was also accomplished in HCl–iPrOH employing 10% Pd/C catalyst.Isopropyl (2R,3S)-3-(3′,4′-bis(benzyloxy)phenyl)-2,3-dihydroxy propanoateC26H31NO6Ee >99.9%[α]D25=-2.0 (c 1, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)(R)-Isopropyl 3-(3′,4′-dihydroxyphenyl)-2-hydroxypropanoateC12H16O5Ee = 97.8%[α]D25=-9.7 (c 1, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (2R)Isopropyl (2S,3R)-3-(3′,4′-bis(benzyloxy)phenyl)-2,3-dihydroxy propanoateC26H31NO6Ee >99.9%[α]D25=+2.0 (c 1, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3R)(S)-Isopropyl 3-(3′,4′-dihydroxyphenyl)-2-hydroxypropanoateC12H16O5Ee = 97.8%[α]D25=+9.7 (c 1, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (2S)

Cinchona alkaloid ester derivatives were adopted to asymmetric dihydroxylation and asymmetric aminohydroxylation reactions in excellent yields and enantiomeric excesses.

Several new octadecylsilyl and polar-modified phases were synthesized. Chromatographic evaluations of these columns were performed using the Dolan and Engelhardt test mixtures. The applicability of these new phases was also evaluated with a mixture of acids, bases or neutral compounds. The distinct differences in the chromatographic behavior between the two groups as well as a high degree of variability within each group were observed. The polar-endcapped phases exhibit similar hydrophobic selectivity, higher hydrogen bonding capacities and silanol activity with reference to C18 columns. The polar-embedded phases display a greatly reduced hydrophobic nature and a significantly reduced silanol activity compared to the C18 phases.