Synthesis of (15E)-17β-hydroxy-5α-androstane-3,15-dione 15-[O-(Carboxymethyl)]oxime, New Hapten for Dihydrotestosterone (17β-hydroxy-5α-androstan-3-one)

1997 ◽  
Vol 62 (10) ◽  
pp. 1642-1649 ◽  
Author(s):  
Ivan Černý ◽  
Tereza Slavíková ◽  
Vladimír Pouzar
Keyword(s):  
Hydroxy Group ◽  
Carboxy Group ◽  
Title Compound ◽  
Oxidative Cleavage ◽  
Hydroxy Derivative ◽  
Borohydride Reduction ◽  
Protecting Group ◽  
Free Hydroxy Group

Addition of 4-methoxybenzyl alcohol to 3β-hydroxy-5α-androst-15-en-17-one gave the mixture of isomeric 15-(4-methoxyphenyl)methoxy derivatives from which, after acetylation and chromatography, the major 15β isomer was separated. Borohydride reduction gave 17β-hydroxy derivative which was protected as methoxymethyl ether. Oxidative cleavage of protecting group at position 15 and the subsequent Jones oxidation afforded corresponding 15-ketone. Its oximation with O-(carboxymethyl)hydroxylamine, deacetylation and methylation with diazomethane gave protected O-(carboxymethyl)oxime derivative with free hydroxy group at position 3. Its oxidation afforded dihydrotestosterone derivative and successive deprotection of position 17 and of carboxy group led to final (15E)-17β-hydroxy-5α-androstane-3,15-dione 15-[O-(carboxymethyl)]oxime. The title compound was designed as dihydrotestosterone hapten for heterologous radioimmunoassays.

The Synthesis of (R)-2',3'-Dihydroxypropyl 5-Deoxy-5-Dimethylarsinyl-β-D-Riboside, a Naturally Occurring Arsenic-Containing Carbohydrate

1987 ◽  
Vol 40 (11) ◽  
pp. 1901 ◽  
Author(s):  
DP Mcadam ◽  
AMA Perera ◽  
RV Stick
Keyword(s):  
Natural Product ◽  
Hydroxy Group ◽  
Title Compound ◽  
Protecting Groups ◽  
Giant Clam ◽  
Free Hydroxy Group ◽  
Naturally Occurring ◽  
Step Procedure ◽  
Tridacna Maxima ◽  
Subsequent Chemical

The synthesis of the title compound, isolated from the brown kelp ( Ecklonia radiata ) or the giant clam (Tridacna maxima), is reported. Glycosidation of 1-O-acetyl-2,3,5-tri- O- benzoyl -β-D-ribose, either directly with (S)-1,2-di-O-benzylglycerol or via the derived orthoester with (S)-1,2-O-isopropylideneglycerol, led to two fully protected glycerol β-D- ribofuranosides. Subsequent chemical manipulations led to a common intermediate having a free hydroxy group at C5 of the D-ribose residue. Replacement of this hydroxy group by a chlorine atom allowed the introduction of the dimethylarsinyl group at C5 in a two-step procedure, and removal of protecting groups provided the natural product.

scholarly journals The crystal structure of 2-[(tert-butyldiphenylsilyl)oxy]-1,2-diphenylethan-1-one

IUCrData ◽  
2019 ◽  
Vol 4 (4) ◽  
Author(s):  
Martin J. Di Grandi ◽  
Brett Taylor ◽  
Peter W. R. Corfield
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Carbonyl Group ◽  
Torsion Angle ◽  
Title Compound ◽  
Borohydride Reduction ◽  
Protecting Group ◽  
Related Molecule ◽  
Compound C

The title compound, C30H30O2Si, was synthesized and structurally characterized in order to determine the influence of the bulky silyl protecting group on the conformation of the benzoin moiety, with a view to directing the stereochemistry of the borohydride reduction of the benzoin. The crystal structure shows a benzoin O—C—C—O torsion angle of 38.34 (1)°, not greatly different from that found in benzoin itself. In the crystal, a weak C—H...O hydrogen bond between the carbonyl group and a phenyl H atom of a symmetry-related molecule forms chains along [100].

scholarly journals Synthetic studies towards d-modified paclitaxel analogues

2012 ◽  
Vol 77 (11) ◽  
pp. 1529-1539
Author(s):  
Zorana Ferjancic ◽  
Radomir Matovic ◽  
Radomir Saicic
Keyword(s):  
Double Bond ◽  
Hydroxy Group ◽  
Oxidative Cleavage ◽  
Protecting Group ◽  
Terminal Double Bond ◽  
Synthetic Sequence ◽  
Sterically Hindered ◽  
Synthetic Studies

A synthetic sequence has been developed for the preparation of 9,10-O-diacetyl-4-desmethylene-4?-(3-butenyl)-4?-hydroxy-5-O-mesyltaxicin I-1,2-carbonate 3, an intermediate in the attempted synthesis of cyclobutane paclitaxel analogue. A series of reactions of 3 has been investigated, including the protection of sterically hindered C-4? hydroxy group and oxidative cleavage of the terminal double bond. Cyclization of 13 to the cyclobutane-containing intermediate failed due to unexpected instability of the DMS protecting group under basic conditions.

Sterically Crowded Heterocycles. VII. Reduction of Some (Z)-1,3-Diphenyl-3-(2-phenylimidazo[1,2-a]pyridin-3-yl)prop-2-en-1-ones as Their Axial Chirality Probe

1996 ◽  
Vol 61 (7) ◽  
pp. 1018-1026 ◽  
Author(s):  
Richard Kubík ◽  
Stanislav Böhm ◽  
Josef Kuthan
Keyword(s):  
Hydroxy Derivative ◽  
Borohydride Reduction ◽  
Axial Chirality ◽  
Pm3 Calculations

Borohydride reduction of titled ketones 1a-1g gave diastereoisomeric mixtures of (Z)-1,3-diphenyl-3-(2-phenylimidazo[1,2-a]pyridin-3-yl)prop-2-en-1-ols 2a-2g and 3a-3g in which the former ones prevailed. Only individual racemic products were obtained after borohydride reduction of (E)-1,3-diphenyl-3-(2-phenylimidazo[1,2-a]pyridin-3-yl)-prop-2-en-1-one 4 to corresponding 1-hydroxy derivative 5 and by conversion of (Z)-1-oxo derivative 1a to 1,3-diphenyl-3-(2-phenylimidazo[1,2-a]pyridin-3-yl)propan-1-one (6) with sodium hydrogenselenide. Diastereoselectivity of the borohydride reduction is discussed using the PM3 calculations of the molecules 1a, 2a, 2b, 3a, 3b, 4, 5, and 6.

The 4-(methylthio)phenyl ester for the synthesis of polypeptides of a known repeating sequence of amino acids. Synthesis of poly-(L-lysylglycyl)glycine 1-C14 ethyl ester hydrobromide

1970 ◽  
Vol 48 (16) ◽  
pp. 2509-2511 ◽  
Author(s):  
Brian J. Johnson ◽  
Donna S. Rea
Keyword(s):  
Amino Acids ◽  
Ethyl Ester ◽  
Title Compound ◽  
Ester Hydrochloride ◽  
Phenyl Ester ◽  
Protecting Group ◽  
High Dilution ◽  
Protective Groups ◽  
Protected Tetrapeptide

The synthesis of the tetrapeptide, N-t-butoxycarbonyl-ε-N-carbobenzoxy-L-lysylglycyl-ε-N-carbobenzoxy-L-lysylglycine 4-(methylthio)phenyl ester is described. The utility of this protective ester is shown by its easy conversion to the protected tetrapeptide 4-(methylsulfonyl)phenyl activated ester without decomposition. Removal of the N-butoxycarbonyl protecting group afforded the polymerizing unit, ε-N-carbobenzoxy-L-lysylglycyl-ε-N-carbobenzoxy-L-lysylglycine 4-(methylsulfonyl)phenyl ester. Polymerization of this material on the partially blocked monomer glycine-1-C14 ethyl ester hydrochloride, at a relatively high dilution, gave poly-(ε-N-carbobenzoxyl-L-lysylglycyl)glycine-1-C14 ethyl ester. The carbobenzoxy protective groups were removed to give the title compound.

scholarly journals Crystal structure of racemic [(1R,2S,3R,4S,6S)-2,6-bis(furan-2-yl)-4-hydroxy-4-(thiophen-2-yl)cyclohexane-1,3-diyl]bis(thiophen-2-ylmethanone)

2016 ◽  
Vol 72 (7) ◽  
pp. 976-979 ◽  
Author(s):  
Ísmail Çelik ◽  
Cem Cüneyt Ersanlı ◽  
Mehmet Akkurt ◽  
Hayrettin Gezegen ◽  
Rahmi Köseoğlu
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Hydroxy Group ◽  
Title Compound ◽  
Furan Ring ◽  
Chair Conformation ◽  
Cyclohexane Ring ◽  
Π Interactions ◽  
Compound C

In the title compound, C28H22O5S3, the central cyclohexane ring adopts a chair conformation. The atoms of the furan ring attached to the 6-position of the central cyclohexane ring are disordered over two sets of sites with occupancies of 0.832 (5) and 0.168 (5). The hydroxy group is disordered over two positions (at the 4- and 6-positions of the cyclohexane ring) in the ratio 0.832 (5):0.168 (5). In the crystal, molecules are linked by C—H...O hydrogen bonds and C—H...π interactions, forming layers parallel to (100).

N-{(2RS)-2-Hydroxy-3-[2-(3-phenylpropanoyl)phenoxy]propyl}propanaminium chloride

2006 ◽  
Vol 62 (5) ◽  
pp. o1694-o1695
Author(s):  
Massimo Bambagiotti-Alberti ◽  
Bruno Bruni ◽  
Ferdinando Costantino ◽  
Massimo Di Vaira ◽  
Valerio Giannellini
Keyword(s):  
Hydrogen Bonds ◽  
Hydroxy Group ◽  
Antiarrhythmic Drug ◽  
Sodium Transport ◽  
Title Compound ◽  
Crystal Packing ◽  
Chloride Ion

The title compound, propafenone hydrochloride, C21H28NO3 +·Cl−, is a potent antiarrhythmic drug, which acts by blocking channels for sodium transport across cell borders. The crystal packing is essentially controlled by a system of hydrogen bonds involving the quaternary N atom, the (disordered) hydroxy group and the chloride ion.

scholarly journals 4-[(E)-(4-Hydroxybenzylidene)amino]-3-methyl-1H-1,2,4-triazole-5(4H)-thione

2014 ◽  
Vol 70 (6) ◽  
pp. o733-o734 ◽  
Author(s):  
Balladka K. Sarojini ◽  
Padmanabha S. Manjula ◽  
B. Narayana ◽  
Jerry P. Jasinski
Keyword(s):  
Hydrogen Bonds ◽  
Intermolecular Interactions ◽  
Hydroxy Group ◽  
Title Compound ◽  
Triazole Ring ◽  
Compound C ◽  
Centroid Distance ◽  
Group Form ◽  
The Mean ◽  
Graph Set

The title compound, C10H10N4OS, is nearly planar with the mean planes of the hydroxybenzyl and triazole rings inclined at an angle of only 3.2 (7)°. In the crystal, O—H...N hydrogen bonds between the hydroxy group and the triazole ring in concert with weak N—H...S intermolecular interactions between the triazole ring and thione group form chains along [-210] enclosingR22(8) graph-set motifs. A weak intramolecular C—H...S interaction and intermolecular π–π interactions [centroid–centroid distance = 3.5990 (15) Å] are also observed.

scholarly journals Synthesis of 6-PEtN-α-D-GalpNAc-(1–>6)-β-D-Galp-(1–>4)-β-D-GlcpNAc-(1–>3)-β-D-Galp-(1–>4)-β-D-Glcp, a Haemophilus influenzae lipopolysacharide structure, and biotin and protein conjugates thereof

2010 ◽  
Vol 6 ◽  
pp. 704-708 ◽  
Author(s):  
Andreas Sundgren ◽  
Martina Lahmann ◽  
Stefan Oscarson
Keyword(s):  
Haemophilus Influenzae ◽  
Surface Antigens ◽  
Amino Group ◽  
Protecting Group ◽  
Primary Position ◽  
Free Hydroxy Group ◽  
Silyl Group ◽  
Protein Conjugates ◽  
Effective Synthesis ◽  
Glycoconjugate Vaccines

Background: In bacteria with truncated lipopolysaccharide structures, i.e., lacking the O-antigen polysaccharide part, core structures are exposed to the immune system upon infection and thus their use as carbohydrate surface antigens in glycoconjugate vaccines can be considered and investigated. One such suggested structure from Haemophilus influenzae LPS is the phosphorylated pentasaccharide 6-PEtN-α-D-GalpNAc-(1→6)-β-D-Galp-(1→4)-β-D-GlcpNAc-(1→3)-β-D-Galp-(1→4)-β-D-Glcp. Results: Starting from a spacer-containing lactose derivative a suitably protected lacto-N-neotetraose tetrasaccharide structure was constructed through subsequential couplings with two thioglycoside donors, a glucosamine residue followed by a galactose derivative, using NIS/AgOTf as promoter. Removal of a silyl protecting group at the primary position of the non-reducing end residue afforded an acceptor to which the terminal α-galactosamine moiety was introduced using a 2-azido bromo sugar and halide assisted coupling conditions. Global deprotection afforded the non-phosphorylated target pentasaccharide, whereas removal of a silyl group from the primary position of the non-reducing end residue produced a free hydroxy group which was phosphorylated using H-phosphonate chemistry to yield the phosphoethanolamine-containing protected pentasaccharide. Partial deprotection afforded the phosphorylated target pentasaccharide with a free spacer amino group but with a protected phosphoethanolamino group. Conjugation of the spacer amino group to biotin or dimethyl squarate followed by deprotection of the phosphoethanolamino group and, in the case of the squarate derivative, further reaction with a protein then afforded the title conjugates. Conclusion: An effective synthesis of a biologically interesting pentasaccharide structure has been accomplished. The target pentasaccharide, an α-GalNAc substituted lacto-N-neotetraose structure, comprises a phosphoethanolamine motif and a spacer aglycon. Through the spacer, biotin and protein conjugates of the title compound have been constructed to allow further use in biological experiments.

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