The application of (S)-1,10-binaphthyl-2,20-diol as NMR chiral solvating agent (CSA) for omeprazole, and three of its analogs (lanso-, panto-, and rabe-prazole) was investigated. The formation of diastereomeric host–guest complexes in solution between the CSA and the racemic substrates produced sufficient NMR signal splitting for the determination of enantiomeric excesses by Hor F-NMR spectroscopy. Using of hydrophobic deuterated solvents was mandatory for obtaining good enantiodiscrimination, thus suggesting the importance of intermolecular hydrogen bonds in the stabilization of the complexes. The method was applied to the fast quantification of the enantiomeric purity of in-process samples of S-omeprazole. Chirality 00:000–000, 2009. VC 2009

The assignment of absolute configuration by NMR

Procedures for the direct replacement of primary hydroxyl groups in carbohydrates by halogen

Assignment of absolute configuration using chiral reagents and NMR spectroscopy.

This invention relates to compositions, compounds and methods for lightening skin, using active compounds having the structure (I) or (II) wherein: (i) each X is, independently, selected from the group consisting of halo, alkyl, substituted alkyl, aryl, OR, OCOR, COR, CONRR, COOR, CN, SR, SOR, SO2R, SO3R and NRR, wherein X is other than hydroxy, amino and thio, if this X is attached ortho to the phenol hydroxy; (ii) m is an integer from 0 to 4; (iii) each R' and R'' is, independently, selected from the group consisting of hydrogen, halo, alkyl, substituted alkyl, aryl, OR, OCOR, OCRROR, COR, CR(OR)OR, CONRR, COOR, CRROR, CN, SR, and NRR; wherein halo, when it appears, is other than geminal to a hydroxy, NH2, or SH; (iv) R''' is alkyl or substituted alkyl; wherein when R''' is present, and R' is also hydrogen, R'' is other than hydrogen, hydroxy, halo, thio, cyano and amino; (v) each R is, independently, selected from the group consisting of hydrogen, alkyl, substituted alkyl and aryl; (vi) n is an integer from 1 to about 5, wherein at least one carbon in (C)n has other than alkyl or hydroxy as a substituent and (C)n adjacent to Z has other than amino, SH, CN or hydroxy as R'; (vii) Z is selected from the group consisting of O, NR, S, SO, SO2, PO2R and POR; (viii) wherein any carbon, when disubstituted, having one substituent selected from the group consisting of hydroxy, amino, cyano and thiol, has the other substituent selected from the group consisting of hydrogen, alkyl, and aryl, whether this substituent is R' or R''; and to pharmaceutically acceptable salts of these compounds, stereoisomers and enantiomers thereof free from or mixed with other enantiomers or stereoisomers; and such compounds in compositions with a pharmaceutically-acceptable carrier thereof comprising a safe and effective amount of a subject skin lightening active.

Skin lightening compositions

Publisher Summary This chapter discusses the chemistry and developments of N -thiocarbonyl carbohydrate derivatives. In N -thiocarbonyl compounds, conjugation of the π-system of the C=S group and the lone pair of nitrogen can take place. This electron-donation effect of N -substituents at thiocarbonyl groups is quite important and stabilizing, more than in the related N -carbonyl derivatives. Consequently, and in contrast to many other thiocarbonyl compounds, thioamides, thioureas, and thiocarbamates are generally very stable and frequently characterizable as crystalline solids. All available X-ray data show unambiguously that the key atoms of N–C(=S) functional groups are situated in a plane, as in the ligands at normal alkenic double bonds, suggesting large contributions from sp 2 ‑hybrid atomic orbitals of the central carbon and nitrogen atoms to the corresponding molecular orbital—that is, a preference for polar resonance structures. The chapter presents the recent developments in the chemistry of N -thiocarbonyl-containing carbohydrate derivatives including isothiocyanates, thioamides, thioureas, thiocarbamates, and dithiocarbamates. It emphasizes on the mutual interactions among the various functional groups that may coexist in a given molecule; their consequences in the structural and chemical properties; and the synthetic, biological, and technical applications of these families of compounds.

Chemistry and developments of N-thiocarbonyl carbohydrate derivatives: Sugar isothiocyanates, thioamides, thioureas, thiocarbamates, and their conjugates

Synthesis of a 6-c-nitro-d-glucopyranose derivative having phosphorus in the hemiacetal ring

Synthesis of 1,2,4-tri-O-acetyl-5-deoxy-5-C-[(R and S)-methoxy-phosphinyl]-3-O-methyl-α- and -β- d-xylopyranose, and their structural analysis by 400-MHz, proton nuclear magnetic resonance spectroscopy

The reactions of diethyl ethylphosphonite with 3-O-acetyl-5-deoxy-5-iodo-1,2-O-isorpopylidine-α-D-xylofuranose (Ia) or 3-O-benzoyl-5-deoxy-5-iodo-1,2-O-isopropylidene-α-D-xylofuranose(Ib) afforded IIa or IIc, respectively. Similarly, using diethyl butylphosphonite in place of diethyl ethylphosphonite, IIb and IId were obtained. Treatment of IIb with methanolic sodium methoxide gave 5-deoxy-1,2-O-isopropylidene-5-(methoxybutylphosphinyl)-α-D-xylofuranose together with a small amount of 5-(3-O-cyclo-butylphosphinate)-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose(VII). Compound VII was also obtained from the reaction of 5-deoxy-5-iodo-1,2-O-isopropylidene-α-D-xylofuranose(VIII) and diethyl butylphosphonite. The reaction of IIa or IIc with sodium dihydrobis(2-methoxyethoxy)aluminate gave 5-deoxy-5-(ethylphosphinyl)-1,2-O-isopropylidene-α-D-xylofuranose(IIIa). Similarly, 5-(butylphosphinyl)-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose(IIIb) was obtained from IIb, IId, VI, and VII. Hydrolysis of IIIa and IIIb ...

Sugars Containing a Carbon-phosphorus Bond. VI. 5-(Alkylphosphinyl)-5-deoxy-D-xylopyranose

A new route for formation of the carbon-phosphorus bond, and synthesis of 1,2,4-tri-O-acetyl-5-deoxy-3-O-methyl-5-C-[(R)- and (S)-phenylphosphinyl]-α- and -β-d-xylopyranose

Kuniaki Seo

Papers

Synthesis of a 6-c-nitro-d-glucopyranose derivative having phosphorus in the hemiacetal ring

Synthesis of 1,2,4-tri-O-acetyl-5-deoxy-5-C-[(R and S)-methoxy-phosphinyl]-3-O-methyl-α- and -β- d-xylopyranose, and their structural analysis by 400-MHz, proton nuclear magnetic resonance spectroscopy

Sugars Containing a Carbon-phosphorus Bond. VI. 5-(Alkylphosphinyl)-5-deoxy-D-xylopyranose

A new route for formation of the carbon-phosphorus bond, and synthesis of 1,2,4-tri-O-acetyl-5-deoxy-3-O-methyl-5-C-[(R)- and (S)-phenylphosphinyl]-α- and -β-d-xylopyranose

Sugars Containing a Carbon-Phosphorus Bond. IV. 5-(Alkylphosphonyl)-5-deoxy- O -methyl- D -xylopyranose