THE REACTION OF UNSATURATED CARBOHYDRATES WITH CARBON MONOXIDE AND HYDROGEN: II. STRUCTURE AND STEREOCHEMISTRY OF THE ANHYDRODEOXYHEXITOLS FROM 3,4-DI-O-ACETYL-D-XYLAL

1964 ◽  
Vol 42 (8) ◽  
pp. 1811-1816 ◽  
Author(s):  
Alex Rosenthal ◽  
Derek Abson
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Magnetic Resonance ◽  
Sodium Borohydride ◽  
Oxidation Product ◽  
Periodate Oxidation ◽  
Borohydride Reduction ◽  
Dicobalt Octacarbonyl ◽  
Sodium Borohydride Reduction

3,4-Di-O-acetyl-D-xylal reacted with carbon monoxide and hydrogen in the presence of dicobalt octacarbonyl to yield 1,5-anhydro-4-deoxy-D-arabino-hexitol (I) and 1,5-anhydro-4-deoxy-L-xylo-hexitol (II). The stereochemistry at C-5 of the hexitols was elucidated by correlation with the triol ether (VI) obtained by sodium borohydride reduction of the periodate oxidation product of 1,4-anhydro-5-deoxy-D-arabino-hexitol (VII). Reaction of 3,4-di-O-acetyl-D-xylal with carbon monoxide and deuterium afforded 1,5-anhydro-4-deoxy-D-arabino-hexitol-4,6,6-H32 (VIII) and 1,5-anhydro-4-deoxy-L-xylo-hexitol-4,6,6-H32 (IX). Examination of the nuclear magnetic resonance (n.m.r.) spectra of the normal and deuterated anhydrodeoxyhexitols confirmed the structural assignments and showed that cis-addition to the double bond takes place to give (IX).

scholarly journals The structure of a glycopeptide purified from porcine thyroglobulin

1971 ◽  
Vol 123 (3) ◽  
pp. 415-420 ◽  
Author(s):  
Minoru Fukuda ◽  
Fujio Egami
Keyword(s):  
Sialic Acid ◽  
Sodium Borohydride ◽  
Periodate Oxidation ◽  
Galactose Oxidase ◽  
Borohydride Reduction ◽  
Enzymic Hydrolysis ◽  
End Groups ◽  
Sodium Borohydride Reduction

1. The structure of a purified glycopeptide isolated from porcine thyroglobulin was studied by sequential hydrolysis with specific glycosidases, by periodate oxidation and by treatment with galactose oxidase. 2. Sequential hydrolysis with several combinations of neuraminidase, α-l-fucosidase, β-d-galactosidase, β-N-acetyl-d-glucosaminidase and α-d-mannosidase presented the evidence for the following structure. 3. The monosaccharide sequence of the peripheral moiety of the heteropolysaccharide chain was sialic acid→galactose→N-acetylglucosamine. Some of the galactose residues were non-reducing end-groups with the sequence galactose→N-acetylglucosamine. 4. After removal of the peripheral moiety composed of sialic acid, fucose, galactose and N-acetylglucosamine, α-mannosidase released 1.4mol of mannose/mol of glycopeptide, indicating that two of the three mannose residues were located between peripheral N-acetylglucosamine and internal N-acetylglucosamine or mannose. 5. Periodate oxidation and sodium borohydride reduction confirmed the results obtained by enzymic degradation and gave information concerning the position of substitution. 6. Based on the results obtained by enzymic hydrolysis and periodate oxidation together with the treatment with galactose oxidase, a structure is proposed for the glycopeptide.

Synthesis of 2-(5',5'-Ethylenedioxy-1'-methylcyclopent-2'-en-1'-yl)ethanol, and Some 2H-Cyclopenta[b]furan Derivatives Formed by Intramolecular Displacement Reactions

1989 ◽  
Vol 42 (1) ◽  
pp. 17 ◽  
Author(s):  
M Campbell ◽  
DJ Collins ◽  
AM James
Keyword(s):  
Double Bond ◽  
Sodium Borohydride ◽  
Lithium Bromide ◽  
Silyl Ether ◽  
Borohydride Reduction ◽  
Ether Group ◽  
Flash Vacuum Pyrolysis ◽  
Vacuum Pyrolysis ◽  
Displacement Reactions ◽  
Sodium Borohydride Reduction

Exchange dioxolanation of 2-methyl-2-(prop-2′-enyl)cyclopentane-1,3-done (1b) gave 3,3- ethylenedioxy-2-methyl-2-(prop-2′-enyl) cyclopentan-1-one (2) which, upon reduction and esterification , afforded the epimeric 3,3-ethylenedioxy-2-methyl-2-(prop-2′-enyl) cyclopent-1-yl benzoates (6d). Oxidative cleavage of the terminal double bond in (6d),followed by sodium borohydride reduction yielded 3,3-ethylenedioxy-2-(2'-hydroxyethyl)-2-methylcyclopent-1-yl benzoate (4b) which underwent acid- catalysed rearrangement to 6a-(2′-hydroxyethoxy)-3a- methylhexahydrocyclopenta [b]furan-4-yl benzoate (8b). Flash vacuum pyrolysis of the t- butyldimethylsilyl ether (12), derived from the hydroxy acetal (4b), afforded 3-[2′- (t- butyldimethylsilyloxy )ethyl]-4,4-ethy1enedioxy-3-methylcyclopent-1-ene (14) which upon selective cleavage of the silyl ether group gave 2-(5′,5′-ethylenedioxy-1′-methylcyclopent- 2'′en-1′-y1)ethanol (7). Reaction of the mesylate (16) of (7) with lithium bromide or iodide in tetrahydrofuran at 50-55� for several hours yielded some of the corresponding 3-(2′-haloethyl) compounds (17), but gave mainly the rearranged 6a-(2′-haloethoxy)-3a-methyl-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furans (19a) and (19b). Some related chemistry is described.

Polybrominated derivatives of 5α-androstane and 5α-estrane 3-ketones: cyclopropanol formation

1976 ◽  
Vol 54 (18) ◽  
pp. 2865-2870 ◽  
Author(s):  
J. F. Templeton ◽  
C. W. Wie ◽  
F. E. Hruska
Keyword(s):  
Magnetic Resonance ◽  
Sodium Borohydride ◽  
Proton Magnetic Resonance ◽  
Spectroscopic Methods ◽  
Borohydride Reduction ◽  
Magnetic Resonance Data ◽  
Resonance Data ◽  
Sodium Borohydride Reduction ◽  
Derivatives Of ◽  
Proton Magnetic Resonance Data

Bromohydrin acetates from sodium borohydride reduction of di- and tribrominated 17β-hydroxy-5α-androstan-3-one and 17β-hydroxy-5α-estran-3-one have been prepared and their structures determined by spectroscopic methods. Some 220 MHz proton magnetic resonance data are reported for structure determination. The formation of cyclosteroid derivatives by 1,3-elimination of bromine with zinc–copper couple is discussed.

A METHOD FOR THE ANALYSIS OF URINARY 17-HYDROXYCORTICOSTEROIDS

1961 ◽  
Vol 22 (1) ◽  
pp. 31-46 ◽  
Author(s):  
J. D. FEW
Keyword(s):  
Sodium Borohydride ◽  
Alkaline Hydrolysis ◽  
Sodium Periodate ◽  
Periodate Oxidation ◽  
Urinary Metabolites ◽  
Partition Chromatography ◽  
Borohydride Reduction ◽  
Urinary Steroids ◽  
Sodium Borohydride Reduction

SUMMARY A method for the analysis of urinary 17-hydroxycorticosteroids is described. The urinary steroids are submitted, in situ, to sodium borohydride reduction, sodium periodate oxidation and mild alkaline hydrolysis. The generated 17-ketosteroids are separated by partition chromatography into 11-deoxy and 11-oxy fractions which are separately estimated by the Zimmermann reaction. By this method it is possible to estimate the urinary metabolites of cortisol without interference by corticosteroids not oxygenated at C-11.

Sign in / Sign up

Export Citation Format

Share Document