A Practical,One-Pot Preparation of Diisopinocampheylchloroborane

A one-pot preparation of the chiral reducing agent diisopinocampheylchloroborane (Ipc₂BCl) from α-pinene and borane methyl sulfide has been developed. The procedure obviates isolation of the air and moisture sensitive reagent, making it useful for large scale operations. Asymmetric reduction of ketones using the in situ prepared Ipc₂BCl is comparable to that using isolated reagent.     

Synthesis of 2′,3′-Dideoxy-2′-Fluorokanamycin A

2′,3′-Dideoxy-2′-fluorokanamycin A (23) was prepared by condensation of 6-azido-4-0-benzoyl-2,3,6-trideoxy-2-fluoro-α-D-ribo-hexopyranosyl bromide (13) and a protected disaccharide (19). Methyl 4,6-0-benzylidene-3-deoxy-β-D-arabino-hexopyranoside (5) prepared from methyl 4,6-0-benzylidene-3-chloro-3-deoxy-β-D-allo-hexopyranoside (1) by oxidation with pyridinium chlorochromate followed by reduction with Na₂ S₂O₄ was fluorinated with the DAST reagent to give methyl 4,6-O-benzylidene-2,3-dideoxy-2-fluoro-β-D-ribo-hexopyranoside (7). Successive treatment of 7 with NBS, NaN₃ and SOBr₂ gave 13. The structure of the final product (23) was determined by the ¹H and ¹⁹F and shift-correlated 2D NMR spectra.     

Synthesis of the Four Configurational Isomers of N-Benzoyl-2, 3, 6-Trtdeoxy-3-C-Methyl-3-Amino-L-Hexose from the (2S, 3R)-Diol Obtained from α-Methylcinnamaldehyde by Fermentation with Baker'S Yeast

Abstract

The erythro and threo chiral C₅ methyl ketones (4) and (5), prepared from the (2S, 3R)-methyl diel (1b), were converted into the phenylsulfenimines (6) and (7), which, in turn, on reaction with allyl-magnesiutn bromide, yielded after acid hydrolysis and benzoylation, the diastereoisomeric C₈-N-aminodiol derivatives (9) and (11), with threo stereochemistry relative to positions 4 and 5. Ozonolysis of (9) and (11) yielded the l-arabino and l-xylo 3-O-methyl branched aminodeoxysugar derivatives (13) and (15), respectively. Using diallylzinc as the reagent, the diastereoisomeric erythro products (8) and (10) were obtained. The latter materials gave the l-ribo-and l-lyxo-(lL-vancosamine) derivatives (12) and (14) upon oxonolysis. The ¹H and ¹³C NMR spectra of the four isomeric aminodeoxysugar derivatives (12)—(15) were discussed.     

Synthesis of (±)-cis-Calamenene;

Hydroboration of 4 furnishes a mixture of primary alcohols 5 and 6. The stereochemistry of the crystalline half ester 7 has been established by X-ray studies. While the oxidation of 5 with Jones reagent furnishes the aldehyde 9 in low yield due to the formation of the by product 3, oxidation with Moffatt reagent furnishes the aldehyde 9 in satisfactory yields. cis-Calamenene 1 has been prepared from 9.     

Reaktionen Mit Trimethylsilylhalogeniden an Derivaten Der Digitoxose

Abstract

Treatment of methyl 3,4-di-O-acyl-2,6-dideoxy-α-D-ribo-hexo-pyranoside 1 or 2 with trimethylsilyl halide leads to the formation of a complex mixture of α-D-ribo-hexopyranosyl halides 3 or 5 together with the educts 1 or 2 as well as their β-anomers 8 or 9. The bromides 3 and 5, suitable for glycosidations, are preferably obtained by reaction of the digitoxose acetate derivatives 6 and 7, respectively, which in turn are prepared from 1 and 2 by mild acetolysis. Further reaction of the halides 3 to 5 with trimethylsilyl halides gives rise to a quantitative formation of the 2,3,6-trideoxy-4-0-acyl-3-halo-α-D -arabino-hexopyranosyl halides 10 to 12. In another reaction sequence starting with the olivose triacetate 20 the formation of 10 via the halide 13 is demonstrated. Structural evidence for the halides 10 to 12 is given by ¹H NMR data as well as by analyses of their glycosides 14 to 19. The results support a mechanistic interpretation for the formation of 10 to 12 via a 3,4-acetoxonium ion as the key intermediate obtained from 3 by an S_Nfi and from 13 and S_N2i step. Final conversion into the terminal halodeoxy compounds 10 to 12 proceeds by and S_N2 reaction with the halide ion.     

Darstellung Der Isomeren 1,6-DI-O-Acetyl-3,4-Didesoxy-α, β-D-Glycero-Hex-3-Enopyrahos-2-Ulosen

Abstract

Prolonged treatment of tetra-O-acetyl-1, 5-anhydro-hex-1-enitols (“tetra-O-acetyl-hydroxy-glycals”) 3 and 5 with BF₃ in CH₂Cl₂ at RT lead to anomeric mixtures of the title compounds 2 and 4a, the α-anomer 4a dominating. Reaction of 5 gave the higher yields of 4a (71%) and 2 (12%), the results being accounted mechanistic grounds. The same reaction performed in an aromatic solvent, like toluene, gave rise to competing C-alkylation., The ortho and para-tolyl derivatives 6 and 7, also with enone structure, were isolated in a combined maximum yield of 40% from 5. β-Enone 2 was also prepared in moderate yield by thermolysis of β-d-glucopyranose pentaacetate (1). In this case no α-anomer 4a was detected.     

Synthesis of O-α-L-Fucopyranosyl-(1→2)-O-β-D-galactopyranosyl-(1→4)-2-acetamido-2-deoxy-D-glucopyranose. The H-Blood Group Specific Trisaccharide

Abstract

Different reaction conditions were investigated for the preparation of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside (5). Compound 5 on reaction with 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide afforded the 4-O-substituted 2-acetamido-2-deoxy-β-D-glucopyranosyl derivative which, on O-deacetylation, gave benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-β-D-glucopyranoside (8). The trimethylsilyl (Me₃Si) derivative of 8, on treatment with pyridineacetic anhydride-acetic acid for 2 days, gave the disaccharide derivative having an O-acetyl group selectively introduced at the primary position and Me₃Si groups at the secondary positions. The latter groups were readily cleaved by treatment with aqueous acetic acid in methanol to afford benzyl 2-acetamido-4-O-(6-O-acetyl-β-D-galactopyranosyl)-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside, which on isopropylidenation gave the desired, key intermediate benzyl 2-acetamido-4-O-(6-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside (12). Reaction of 12 with 2,3,4-tri-O-benzyl-α-L-fucopyranosyl bromide under catalysis by bromide ion afforded the trisaccharlde derivative from which the title trisaccharide was obtained by systematic removal of the protective groups. The structures of the final trisaccharide and of various intermediates were established by ¹H and ¹³C NMR spectroscopy.     

Synthesis of Fluorinated Dienylic Stannanes Via the Wadsworth-Emmons Reaction

Geminal difluorination of dithiolane 9 affords bis benzyl ether 4b which is converted to beta-fluoroenals 3Z/3E. Reaction of these enals with the stannylmethyl Wadsworth-Emmons reagent 2 produces dienyl esters 14Z/14E which are converted to highly functionalized dienylic stannanes 1Z and 1E.     

A Conventient Synthesis of 3-Hydroxy-4-chromanone Using Iodobenzene Diacetate

A useful synthesis of 3-hydroxy-4-chromanone (6) is not currently available. Lead tetraacetate oxidation of 4-chromanone (4) yields the C(3) acetoxy derivative but this compound could not be deacetylated to 6.¹ Recently Donnelly and Maloney reported² that the Algar-Flynn-Oyamada reaction (H₂O₂/CH₃OH/NaOH), which is commonly used for the conversion of o-hydroxychalcones (1) into 3-hydroxyflavanone (2) and 3-hydroxyflavones (3), does not yield 6 when applied to o-hydroxya-crylophenone 1 (R = H). The authors found that under less basic conditions using K₂CO₃ some 6 is formed but the major product is catechol. These observations clearly indicate the necessity of developing a method for making 6. The present note describes a staightforward way of preparing 3-hydroxy-4-chromanone (6) in good yield.     

REACTIONS OF DITHIOLETHIONES WITH N,N-DICHLOROAMIDES

Abstract

Dependent on the starting materials and the reaction conditions N,N-dichloroamides Cl₂N-X (X = COaryl, CO₂alkyl, SO₂aryl, SO₂N(alkyl)₂) react with dithiolethiones 1 and 5 to N-(dithiolyliden)amides 2, 6, S-(dithiolylidene)sulfimides 3, thionoxides 7 and dithiolones 4, 8. The mechanisms have been studied.     

Role of the Polymer Backbone in the Oxidative Properties of Polymer-Supported Dichromate

Crosslinked co/poly(styrene-4-vinylpyridine)/ (1) was converted with hydrogen bromide or alkyl bromide to a pyridinium salt (2) which was further converted in water medium to various immobilized dichromates (3) with CrO₃. The insoluble reagent containing 0.6–1.0 mmol of dichromate on a gram of resin (depending on the structure of the polymer backbone) oxidized several secondary alcohols to ketones. The rate of conversion of alcohols to ketones depended on the structure of the polymer backbone, the structure of the alcohol, and the amount of water (5% or 20%) occluded in the reagent 3.     

Stereoselective Synthesis of 3-C-Branched-Chain Sugars by Aldol Reaction of Furanos-3-Uloses with Acetone

Abstract

Aldol reaction of 1,2-O-isopropylidene-5-O-tertbutyl-dimethylsilyl-α-D-erythro-pentofuranos-3-ulose (1) with acetone in the presence of aqueous K₂CO₃ afforded 3-C-acetonyl-1,2-O-isopropylidene-5-O-tertbutyl-dimethylsilyl-α-D-ribofuranose(2). Similar reaction of 1,2:5, 6-di-o-isopropylidene- α-D-ribo-hexofuranos-3-ulose (3) afforded 3-C-acetonyl-1,2:5, 6-di-o-isopropylidene- α-D-allofuranose (4) and (1R, 3R, 7R, 8S, 10R)-perhydro-8-hydroxy-5,5,10-trimethyl-2,4,6,11,14-pentaoxatetracyclo[8,3,1,0^1,8,0^3,7] tetradecane. The stereochemistry of the new chiral centers were determined by ¹H NOE experiments.     

An Improved Synthesis of Ethyl Azodicarboxylate and 1,2,4-Triazoline-3,5-Diones Using Hypervalent Iodine Oxidation

ARSTRACT: Hypervalent iodine oxidstion of 1,2-dicarhethoxy hydrazine (1) and 4-substituted urazoles (3) using iodobenzene diacetate or pentafluoroiodobenzene bis-trifluoroacetate in CH₂Cl₂ at room temperature proceeds smoothly to yield ethyl azodicarboxylate (2) and 4-substituted 1,2,4-triazoline-3,5-diones (4) in excellent yields.     

Reactions of α-Hydroxyphosphonates under PTC Conditions

Abstract

We found, that dialkyl phosphite 1 and oxo-compound 2 in an equilibrium reaction give an adduct α-hydroxyphosphonate 5 un -der phase-transfer catalytic conditions [K₂CO₃/TEBA/dichloroethane or aromatic solvents (solid-liquid PTC); 50% NaOH/TEBA/dichloroethane or benzene (liquid-liquid PTC)]. On the other hand 3, is transformed to phosphate 4 or to α-alkoxyphosphonate 5 in the presence of alkylating agent using PTC circumstances.     

Use of 1-Penten-3-One-4- Phosphonate as a Kinetic Ethyl Vinyl Ketone Equivalent in the Robinson Annulation Reaction1

Reaction of cross-conjugated silyl dienol ether 4 with the title reagent affords adduct 9. Epoxidation of 9 provides α–epoxy ketone 10. Both keto–phosphonates 9,10 undergo smooth intramolecular Wadsworth–Emmons reactions to produce enones 2,3.     

Solvolysis of 9-Bromo-ω-bromolongifolene/9-bromo-longifolene: Synthesis of Longi-β-Nozigiku Alcohol/Longicyclenyl Alcohol from Japanese Sugi/Hinoki Essential Oils

Longi-β-nozigiku alcohol 3/longicyclenyl alcohol 4 reported in Japanese sugi/hinoki essential oils, have been synthesized from longicyclene 2 using bromination as the key step. 9-Bromo-ω-bromo longifolene 5 (prepared from 2 by action of pyridine perbromide) is exposed to silver perchlorate in aqueous acetone to afford the ω-bromo-alcohol 7; refluxing 3. with Na-t-BuoH-THF gives the homoallylic alcohol 3. Solvolysis of 9-bromolongifolene 6 (prepared by bromination of 2 with NBS in CHCl₃ at reflux) with KOAc in ACOH at 75°/4 hr followed by hydrolysis furnishes longicyclenyl alcohol 4.     

The Synthesis of Hydronaphthalenes from m-Toluic Acid via Cyclization of Thioacetal Monosulfoxides

We recently developed a convenient route to hexahydronaphthalenols such as 5 (R=CO₂CH₃ or CH₃) starting from m-toluic acid (1)¹. The key features of the route involved reduction-alkylation of the toluic acid to the dihydro derivative 2 ², subsequent deprotection and oxidation of the side chain primary alcohol, and acid-catalyzed cyclization of the resulting aldehyde 4. In the case of the dimethylnaphthalenols 5 (R=CH₃), conversion of the angular carboxylic function to the methyl group was effected prior to cyclization via reduction of the p-toluenesulfonic ester of the neopentyl alcohol 3 (R=CH₂OH) using lithium triethylborohydride³.     

SRN1 Arylation of Some Heterocyclic Ketene Aminals with 2,4-Dinitrohalobenzenes

the anion of heterocyclic ketene aminals 1 - 4 reacted with 2, 4-dinitrohalobenzenes 5 to give the monoarylated products 6, 7, 9 and 11 by a S_RN1 mechanism. In some cases, the diarylated products 8 and 10 were also isolated.     

Destruction of Toxic Organophosphorus Esters by Oxidative α-Nucleophilic Reagent

Abstract

Despite its self-decomposition, Magnesium MonoPeroxyPhtalate 4 is an excellent reagent to totally detoxify phosphonothiolate 1 and fluoridate 2 in basic aqueous medium.     

Synthesis of Gentamine C1a from Neamine Using Ionic Displacement and Radical Elimination Methods

Abstract

The conversion of tetra-N-benzyloxycarbonyl-5,6-O-cyclohexylidene neamine (8) into the corresponding olefin 13 has been investigated by three methods. Application of the Tipson-Cohen procedure via the dimesylate 10 gave a low yield (22%), as did the reaction of the diol 8 with triphenylphosphine-iodine-imidazole reagent (42%). Contrastingly, reductive radical elimination via the dixanthate 11 gave a synthetically useful yield (64%) without any chromatographic purification.