Synthesis of N-benzoyl-L-daunosamine from D-threonine

The synthesis of N-benzoyl-$\text{L}$-daunosamine (14) from the C₄$\text{threo}$ aldehyde (2b), prepared from $\text{D}$-threonine, through the intermediacy of the C₇ adduct (7a) is reported     

Reversal of diastereofacial selectivity in the intramolecular michael addition of -α-carbamoyloxy-α,β-unsaturated esters. Synthesis of N-benzoyl-D,L-daunosamine

Contrary to the precedents, 1,3-anti stereoselection was found in the intramolecular Michael addition of ethyl $\text{threo}$,5-carbamoyloxy-4-trialkylsilyloxy-2-hexenoate to culminate in a synthesis of N-benzoyl-$\text{D}$,$\text{L}$-daunosomine. The antiperiplanar effect due to the group at 4-position was revealed to play a major role in the stereoselection in this type of reactions. N-benzoyl-$\text{D}$,$\text{L}$-3-epidaunosamine was also synthesized by 1,2-syn asymmetric induction.     

Synthesis of N-benzoyl L- and D-2,3,6-trideoxy-3-aminoxylo-hexose from non-carbohydrate precursors

The enantiomeric alcohols ($\text{2}$) and ($\text{11}$), obtained from (2$\text{R}$,3$\text{R}$) tartaric acid and, respectively, $\text{L}$-threonine, have been used to construct the C₆, enantiomeric deoxy amino sugar derivatives ($\text{7}$) and ($\text{12}$)     

Total synthesis of the disaccharide of bleomycin, 2-0-(α-D-mannopyranosyl)-L-gulopyranose

2-0-(α-$\text{D}$-Mannopyranosyl)-$\text{L}$-gulopyranose, the sugar portion of bleomycin has been synthesized.     

Boat-chair conformational preference of exo, exo-9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid

The ¹H and ¹³C nmr spectra of $\text{exo}$, $\text{exo}$-9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid, 3, in DMSO-d₆ or alkaline D₂O, clearly show that it exists in a $\text{boat}$-$\text{chair}$-conformation with $\text{equatorial}$ carboxyl groups, thus being the first case of $\text{boat}$-$\text{chair}$ preference of a bicyclo[3.3.1] nonan-9-one due to the presence of $\text{exo}$,$\text{exo}$-2,4- substituents.     

[2+2] Cycloaddition of benzyne to cis,trans- and cis,cis-1,5-cyclooctadiene

The relative rates of formation of $\text{cis}$ and $\text{trans}$ [2+2]cycloadducts of benzyne to $\text{cis}$, $\text{trans}$- and $\text{cis}$, $\text{cis}$-1,5-cyclooctadiene, $\text{trans}$- and $\text{cis}$-cyclooctene are discussed and properties of the adducts (e.g., their unusual hydrogenation) are described.     

Autorecycling oxidation of alcohol catalyzed by 1,3,7,9,11,12,14-heptazapentacene-2,4,8,10 (14H,3H,9H,12H)-tetraones (mixed flavins)

1,3,7,9,11,12,14-Heptazapentacene-2,4,8,10 (14$\text{H}$,3$\text{H}$,9$\text{H}$,12$\text{H}$)-tetraones (mixed flavins) were prepared by the cyclization of 1,5-dihydro-8-[N-alkyl-N-(5-nitrouracil-6-yl)-amino-5-deazaflavins with Vilsmeier reagent. The mixed flavins oxidized alcohol under neutral condition in sunlight and a remarkable autorecycling was observed.     

13C-NMR spectra of 6-aminohexyl glycosides of O-β-D-galactopyranosyl-2-acetamido-2-deoxy-β-D-glucopyranose

¹³C-NMR spectral data on 6-aminohexyl glycosides of $\text{O}$-β-$\text{D}$-galactopyranosyl-2-acetamido-2-deoxy-β-$\text{D}$-glucopyranose are pr     

Synthesis of N-benzoyl-L-ristosamine

The synthesis of N-benzoyl-$\text{L}$-ristosamine (7) from natural tartaric acid through the intermediacy of the δ-$\text{xylo}$ and γ-$\text{ribo}$ lactones (4) and (6) is reported.     

Synthesis of (1s,5r)-karahana ether and (1s,5r)-karahana lactone,the optically active forms of unique monoterpenes wit

(1$\text{S}$,5$\text{R}$)-(-)-Karahana ether (8,8-dimethyl-2-methylene-6-oxabi-cyclo[ 3.2.1]octane) and (1$\text{S}$,5$\text{R}$)-(-)-karahana lactone (8,8-dimethyl-2-methylene-6-oxabicyclo [3.2.1]octan-7-one) were synthesized from ($\text{S}$)-3-hydroxy-2,2-dimethylcyclo-hexanone. The natural karahana lactone was shown to be almost racemic ($\text{ca}$. 1.3 % e.e.).     

Stereoselective synthesis of (1R,3R,5S-1,3-dimethyl-2,9-dioxabicyclo[3.3.1]nonane

(1$\text{R}$,3$\text{R}$,5$\text{S}$)-1,3-Dimethyl]-2,9-dioxabicyclo[3.3.1]nonane $\text{1}$ has been stereoselectively synthesized based on a highly stereoselective method for the synthesis of 1,3-$\text{syn}$-polyol.     

Steroidal antifeedants from the dorid nudibranch Aldisasanguineacooperi

Two steroids, 3-oxo-chol-4-ene-24-oic acid ($\text{2}$) andi ts unsaturated analog $\text{4}$ have been isolated from the dorid nudibranch $\text{Aldisa}$$\text{sanguinea}$$\text{cooperi}$, and the acid $\text{2}$ has been shown to have antifeedant properties.     

A short synthesis of (s)-5-hydroxymethyl-(5h)-furan-2-one and derivatives from d-ribonolactone

We describe a short synthesis of ($\text{S}$)-5-hydroxymethyl-(5$\text{H}$-furan-2-one and some 5-O-derivatives, which are being used as key starting products for the synthesis of several antileukaemic lignan lactones, from $\text{D}$-ribonolactone.     

The sterepolides: new isolactaranes from stereumpurpureum

Sterepolide and dihydrosterepolide, new sesquiterpenes isolated from the fungus $\text{Stereum}$$\text{purpureum}$, are assigned structures $\text{4}$ and $\text{7}$, respectively. The assignments are based mainly on spectroscopic studies and similarities to isolactarorufin ($\text{5}$). A possible mode of biogenesis of these isolactarane type sesquiterpenes is discussed.     

A novel synthesis of 5-thio-D-glucose

A shorter synthesis of 5-thio-$\text{D}$-glucose is described in 8 steps from commercially available $\text{D}$-glucofurano-3,6-lactone.     

Z,Z-dienes via acetylene carbocupration: synthesis of navel orangeworm pheromone

A range of conjugated $\text{Z}$,$\text{Z}$-dienes have been prepared in a stereo-specific manner $\text{via}$ acetylene carbocupration: the value of this procedure has been illustrated by an extremely short synthesis of hexadeca-11$\text{Z}$, 13$\text{Z}$-dienal a principle component of Navel Orangeworm Pheromone.     

Olefin metathesis in polycyclic frames 1. A new way to cis, syn, cis - tricyclopentanoids (acs-C11-triquinanes)

A novel olefin metathesis sequence permits ready access to functionalised $\text{cis}$, $\text{syn}$, $\text{cis}$-tricyclo [6.3.0.0^2,6] undecane based bis-enones. These bis-enones have been shown to undergo cage cyclisation in sunlight with remarkable ease and efficiency.     

Synthesis of the enantiomeric forms of cis and trans 1-benzyloxy-2,3-epoxy butane and of (3S,4S) 4-methyl-3-heptanol

The C₄erythro and threo diols (7) and (8) are converted either into the chiral epoxides (13) and (15) or into the enantiomers (14) and (16); the epoxide (13) is used as chiral synthon for the preparation of (3$\text{S}$,4$\text{S}$) 4-methyl-3-heptanol (21).     

Synthesis of β-d-mannopyranosides and regioselective o-alkylation of dibutylstannylene complexes

Alkylation of dibutylstannylene complexes of 3,4,6-tri-$\text{O}$-benzyl-$\text{D}$-mannopyranose, methyl 6-$\text{O}$-trityl-α-$\text{D}$-mannopyranoside and methyl α-$\text{D}$-mannopyranoside gives respectively β-$\text{D}$-mannopyranoside and 3-$\text{O}$-alkyl derivatives with high selectivity.     

Preparation of halo-F-methanes via potassium fluoride-halogen cleavage of halo-F-methylphosphonium salts

Treatment of halo-$\text{F}$-methylphosphonium salts with potassium fluoride and halogen (I₂, Br₂, ICl, IBr) gives modest yields of halo-$\text{F}$-methanes. This method of preparation augments the classical Hunsdiecker approach to these materials.