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1.
Thermolysis of the glycosylidene-derived O-benzylated diazirine 1 in the presence of N-phenylmaleimide ( 2 ), acrylonitrile ( 3 ), dimethyl fumarate ( 4 ), or dimethyl maleate ( 5 ) led in good yields to mixtures of the spirocyclopropanes 6 / 7 , 8 – 11 , 12 / 13 , and 12 / 13 / 16 / 17 . The diastereoselectivity depends upon the alkene. The cycloaddition of 1 to 5 is not diastereospecific, in keeping with previous results. Deprotection of 12 , 13 , 16 , and 17 yielded the tetrols 14 , 15 , 18 , and 19 , respectively.  相似文献   

2.
The diastereoselectivity of the addition of NH3 and MeNH2 to glyconolactone oxime sulfonates and the structures of the resulting N‐unsubstituted and N‐methylated glycosylidene diaziridines were The 15N‐labelled glucono‐ and galactono‐1,5‐lactone oxime mesylates 1* and 9* add NH3 mostly axially (>3 : 1; Scheme 4), while the 15N‐labelled mannono‐1,5‐lactone oxime sulfonate 19* adds NH3 mostly equatorially (9 : 1; Scheme 7). The 15N‐labelled mannono‐1,4‐lactone oxime sulfonate 30* adds NH3 mostly from the exo side (>4 : 1; Scheme 9). The configuration of the N‐methylated pyranosylidene diaziridines 17, 18, 28 , and 29 suggests that MeNH2 adds to 1, 9, 19 , and 23 mostly to exclusively from the equatorial direction (>7 : 3; Schemes 5 and 8). The mannono‐1,4‐lactone oxime sulfonate 30 adds MeNH2 mostly from the exo side (85 : 15; Scheme 10), while the ribo analogue 37 adds MeNH2 mostly from the endo side (4 : 1; Scheme 10). Analysis of the preferred and of the reactive conformers of the tetrahedral intermediates suggests that the addition of the amine to lactone oxime sulfonates is kinetically controlled. The diastereoselectivity of the diaziridine formation is rationalized as the result of the competing influences of intramolecular H‐bonding during addition of the amines, steric interactions (addition of MeNH2), and the kinetic anomeric effect. The diaziridines obtained from 2,3,5‐tri‐O‐benzyl‐D ‐ribono‐ and ‐D ‐arabinono‐1,4‐lactone oxime methanesulfonate ( 42 and 48 ; Scheme 11) decomposed readily to mixtures of 1,4‐dihydro‐1,2,4,5‐tetrazines, pentono‐1,4‐lactones, and pentonamides. The N‐unsubstituted gluco‐ and galactopyranosylidene diaziridines 2, 4, 6, 8 , and 10 are mixtures of two trans‐substituted isomers ( S / R ca. 19 : 1, Scheme 2). The main, (S,S)‐configured isomers S are stabilised by a weak intramolecular H‐bond from the pseudoaxial NH to RO? C(2). The diaziridines 12 , derived from GlcNAc, cannot form such a H‐bond; the (R,R)‐isomer dominates ( R / S 85 : 15; Scheme 3). The 2,3‐di‐O‐benzyl‐D ‐mannopyranosylidene diaziridines 20 and 22 adopt a 4C1 conformation, which does not allow an intramolecular H‐bond; they are nearly 1 : 1 mixtures of R and S diastereoisomers, whereas the OH5 conformation of the 2,3:5,6‐di‐O‐isopropylidene‐D ‐mannopyranosylidene diaziridines 24 is compatible with a weak H‐bond from the equatorial NH to O? C(2); the (R,R)‐isomer is favoured ( R / S ≥7 : 3; Scheme 6). The mannofuranosylidene diaziridine 31 completely prefers the (R,R)‐configuration (Scheme 9).  相似文献   

3.
The benzyl- and the acyl-protected glyconolactone tosylhydrazones 6 , 9 , 12 , 16 , and 19 (Scheme 1) were prepared in good yields by treating the hemiacetals 4 , 7 , 10 , 14 , and 17 with N-tosylhydrazine, to give the N-glycosylhydrazines 5 , 8 , 11 , 15 , and 18 , and by oxidizing these hydraz tries with N-bromosuccinimide (NBS) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), with CrO3–dipyridine complex or with pyridinium dichromate. Photolysis of the sodium sail 20 of 6 (Scheme 2) in the presence of N-phenylmaleimide, dimethyl fumarate, or acrylonitrile gave the corresponding cyctopropanes 21 – 28 in satisfactory yields. Phololytic or thermolytic glycosidation of phenol and 4-melhoxyphenol by 20 yielded the anomeric glycosides 29 / 30 and 31 / 32 , yields being marginally higher for the Ihermolytic process. Phololytic glycosidation of propan-2-ol gave the glycosides 33 and 34 in low yields only. Yields and ratios of products were compared to those obtained with the diazirine 1 as a source of glycosylidene carbenes. While the yields from 20 are lower, the ratios of products obtained in the photolytic reactions are in agreement with the formation of a common intermediate from both carbene precursors.  相似文献   

4.
Acylation and sulfonylation of the N,Nunsubstituted glucosylidenespirodiaziridines 1A / 1B 95 : 5 with Ac2O, BzCl, FmocCl, TsCl, (naphthalen‐2‐yl)sulfonyl, and (2,4,6‐triisopropylphenyl)sulfonyl chloride, and concomitant rearrangement gave the acylated and sulfonylated gluconolactone hydrazones 2B – 2G in 40–83% yield (Scheme 2). Similarly, the galacto and manno analogues 3A / 3B 95 : 5 and 5A / 5B 55 : 45 and the mannofuransoylidene‐diaziridine 30 were acetylated and tosylated to give 4A, 4B, 6, 31A , and 31B (55–73% yield; Schemes 2 and 5). 15N‐Labelling of 11A / 11B and 14A / 14B showed that the pseudoequatorial NH of the gluco diaziridines 1 and the pseudoaxial NH of the galacto diaziridines 3 were preferentially acetylated and tosylated (Scheme 3). Sulfonylation of the N‐methylated diaziridines 19A / 19B 72 : 28, 22A / 22B 85 : 15, 25A / 25B 85 : 15, 28A / 28B 80 : 20, and 33A / 33B / 33C / 33D 76 : 4 : 12 : 8 yielded the N‐methyl‐N‐tosylglyconolactone hydrazones 20, 23, 26, 29 , and 34 (44–66%; Schemes 4 and 5). The methylated N‐atom of the diaziridines proved more reactive, irrespective of the configuration at C(2) and C(4). The products were readily hydrolysed to glyconolactones.  相似文献   

5.
Phenol, 4-methoxyphenol, 4-nitrophenol, methyl orsellinate ( 1 ), and 2,6-di(tert-butyl)-4-methylphenol (BHT; 2 ) have been glycosylated by thermal reaction (20–60°) with various glycosylidene-derived diazirines. 4-Methoxyphenol reacted with the D-glucosylidene-derived diazirine 3 to give O-glucosides ( 4 and 5 , 69%, 3:1) and C-glucosides ( 6 and 7 , 16%, 1:1). Similarly, phenol yielded O-glucosides ( 10 and 11 , 70%, 4:1) and C-glucosides ( 12 and 13 , 13%, 1:1). 4-Nitrophenol gave only O-glycosides, 3 leading to 14 and 15 (75%, 3:2; Scheme 1), and the D-galactosylidene-derived diazirine 17 to 22 and 23 (52% (from 16 ), 65:35; Scheme 2). The reaction of phenol with 17 yielded 58% (from 16 ) of the O-galactosides 18 and 19 (4:1) and 14% of the C-galactosides 20 and 21 (1:1). From the D-mannosylidene-derived diazirine 25 , we predominantly obtained the α-D-configurated 26 (38 % from 24 ). These results are interpreted by assuming that an intermediate (presumably a glycosylidene carbene) first deprotonates the phenol to generate an ion pair which combines to give O- and - with electron-rich phenolates - also C-glycosides. A competition experiment of 3 with 4-nitro- and 4-methoxyphenol gave the products from the former ( 14 and 15 ) and the latter phenol ( 4-7 ) in almost equal amounts. Differences in the kinetic acidity of OH groups, however, may form the basis of a regioselective glycosidation, as evidenced by the reaction of 3 with methyl orsellinate ( 1 ) yielding exclusively the 4-O-monoglycosylated products 27 and 28 (78%, 85:15), although diglycosidation is possible ( 27 → 31 and 32 ; 67%, 4:3; Scheme 3). Steric hindrance does not affect this type of glycosidation; 3 reacted with the hindered BHT ( 2 ) to afford 33 and 34 (81 %, 4:1). The predominant formation of 1,2-trans -configurated O-aryl glycosides is rationalized by a neighbouring-group participation of the 2-benzyloxy group.  相似文献   

6.
The syntheses of glycosides from the diazirine 1 and a range of alcohols under thermal and/or photolytic conditions are described. Yields and diastereoselectivities depend upon the pKHA values of the alcohols, the solvent, and the reaction temperature. The glycosidation of weakly acidic alcohols (MeOH, EtOH, i-PrOH, and t-BuOH, 1 equiv. each) in CH2Cl2 at room temperature leads to the glycosides 2–5 in yields between 60 and 34% (Scheme 1 and Table 1). At ?70 to ?60°, yields are markedly higher. In CH2Cl2, diastereoselectivities are very low. In THF, at ?70 to ?60°, however, glycosidation of i-PrOH leads to α-D -/β-D - 4 in a ratio of 8:92. More strongly acidic alcohols, such as CF3CH2OH, (CF3)2 CHOH, and (CF3)2C(Me)OH, and the highly fluorinated long-chain alcohols CF3(CF2)5(CH2)2OH ( 11 ) and CHF2(CF2)9CH2OH ( 13 ) react (CH2Cl2, r.t.) in yields between 73 and 85% and lead mainly to the β-D -glucosides β-D - 6 to β-D - 8 , β-D - 12 , and β-D - 14 (d.e. 14–68%). Yields and diastereoselectivities are markedly improved, when toluene, dioxane, 1,2-dimetoxyethane, or THF are used, as examined for the glycosidation of (CF3)2C(Me)OH, yielding (1,2-dimethoxyethane, 25°) 80% of α-D -/ β-D - 8 in a ratio of 2:98 (d.e. 96%; Table 4). In EtCN, (CF3)2C(Me)OH yields up to 55% of the imidate 10 . Glycosidation of di-O-isopropylideneglucose 15 leads to 16 (CH2Cl2, r.t.; 65%, α-D / β-D = 33:67). That glycosidation occurs by initial protonation of the intermediate glycosylidene carbene is evidenced, for strongly acidic alcohols, by the formation of 10 , derived from the attack of (CF3)2MeCO? on an intermediate nitrilium ion (Scheme 4), and for weakly acidic alcohols, by the formation of α-D - 9 and β-D - 9 , derived by attack of i-PrO? on intermediate tetrahydrofuranylium ions. A working hypothesis is presented (Scheme 3). The diastereoselectivities are rationalized on the basis of a protonation in the σ plane of the intermediate carbene, the stabilization of the thereby generated ion pair by interaction with the BnO? C(2) group, with the solvent, and/or with the alcohol, and the final nucleophilic attack by RO? in the π plane of the (solvated) oxonium ion.  相似文献   

7.
In the context of the hypothesis postlating a heterolytic cleavage of a C? N bond during thermolysis of alkoxydiazirines (Scheme 1), we report the preparation of the diazirines 4 , 5 , 7 , and 8 , the kinetic parameters for the thermolysis in MeOH of the diazirines 1 and 4–9 , and the products of their thermolysis in an aprotic environment. The diazirines 4 , 57 , and 8 (Scheme 2–5) were prepared from the known hemiacetals 10 , 19 , 34 (prepared from 31 in an improved way), and 42 according to an established method. The oximes 11 , 20 , 35 , and 43 were obtained from the corresponding hemiacetals as (E/Z)-mixtures; 43 was formed together with the cyclic hydroxylamine 44 . Oxidation of 11 , 35 , and 43 (N-chlorosuccinimide/1,8-diazabicyclo[5.4.0]undec-7-ene (NCS/DBU) or NaIO4) gave good yields of the (Z)-hydroximolactones 12 , 36 , and 45 , while the oxime 20 led to a mixture of the (E)- and (Z)-hydroximolactones 21 and 22 , which adopt different conformations. Their configuration was assigned, inter alia, by a comparison with the enol ethers 28 and 29 , which were obtained, together with 30 , from the reaction of the diazirine 5 with benzaldehyde and PBu3. Treatment of the hydroximolactone O-sulfonates 13 , 23 , 37 , and 46 with NH3/MeOH afforded the diaziridines 15 , 25 , 38 , and 47 in good yields, while the (E)-sulfonate 24 decomposed readily. Oxidation of the diaziridines gave 4 , 5 , 7 , and 8 , respectively. Thermolysis of the diazirines 1 and 4–9 in MeOH yielded the anomeric methyl glycosides 50/51 , 16/17 , 26/27 , 52/53 , 39/40 , 48/49 , and 54/55 , respectively. A comparison of the kinetic data of the thermolysis at four different temperatures shows the importance of conformational and electronic factors and is compatible with the hypothesis of a heterolytic cleavage of a C? N bond. An early transition state is evidenced by the absence of torsional strain by an annulated 1,3-dioxane ring. Thermolysis of 1 in MeCN at 23° led mostly to the diasteroisomeric (Z,Z)-, (E,E)-, and (E,Z)-lactone azines 56 , 57 , and 58 (Scheme 6), which convert to 56 under mild conditions, and to 59 (3%). The benzyloxyglucal 59 was obtained in higher yields (18%), together with 44% of 56–58 , by thermolysis of solid 1 . Similarly, thermolysis at higher temperatures of 4 in toluene, THF, or dioxane and of 9 in CH2Cl2 or THF yielded the (Z,Z)-lactone azines 60 and 61 , respectively, the latter being accompanied by the dihydro-oxazole 62 .  相似文献   

8.
Mannosylidenation of buckminsterfullerene (C60; 1 ) with the 2,3-di-O-benzyl-4,6-O-benzylidene-protected diazirine 7 and the 2,3:4,6-di-O-isopropylidene-protected diazirine 8 leads to the spiro-linked C -glycosides 6 and 10 in 44 and 31% yield, respectively (Scheme). The diazirine 8 was prepared in five steps from 2,3:4,6-di-O-iso-propylidene-α-D -mannopyranose ( 11 ) via the oximes 12 , the (Z)-hydroximolactone 13 , the mesylate 14 , and the diaziridines 15 . Deprotection of the mannosylidenated fullerenes 6 and 10 under acidic conditions gave the partially deprotected diol 9 (97%) and the unprotected mannosylidenated fullerene 16 (73%), respectively. The mannosylidene-fullerenes 6, 9, 10 , and 16 possess a 6–6 ring-bridged σ-homoaromatic structure.  相似文献   

9.
Glycosidation by the diazirine 1 , the trichloroacetimidate 4 , and the bromide 5 of the altro-diol 2 , possessing an intramolecular H-bond (HO? C(3) to O? C(1)) in solution, but not in the solid state, proceeds with high and complementary regioselectivity. From 2 and 1 , one obtains mostly the 1,2-linked disaccharides 10 and 11 (β-D > α-D ), together with the 1,3-linked isomers 12 and 13 (α-D > β-D ; 1,2-/1,3-linked products ca. 9:1), the demethylated 1,3-linked disaccharides 24–27 , the trisaccharides 19–22 , the lactone azines 23 , and the hydroxyglucal 18 , while 2 reacted with 4 or 5 to yield mostly the 1,3-linked disaccharides (1,2-/1,3-linked products ca. 1:9). The disaccharides were additionally characterized as acetates (→ 14–17, 28–31 ). Yields and stereoselectivity depended upon the donor, stoichiometry, solvent, temperature, and concentration. Glycosidation of the 1,3-linked disaccharides with 1 yielded the trisaccharides 19–22 . Reaction of the β-D -altro-diol 3 with 1 gave the 1,2- and 1,3-linked disaccharides 32/33 and 34/35 in a 1:1 ratio, characterized as the acetates 36–39 , while glycosidation with 5 according to Lemieux proceeded regioselectively (1,2-/1,3-linked products 91:9). The monotosylates 6 and 7 reacted with 1 to yield the anomeric pairs 40/41 , and 42/43 of the tosylated disaccharides; the oxiranes 44 and 45 were not observed.  相似文献   

10.
Ginkgolide B ( 1b ) has been glucosylated in THF with the glucosylidene-derived diazirine 2 under thermal or photochemical conditions. Depending on the amount of 2 , we obtained either monoglucosides ( 5 – 8 ), diglucosides ( 13 – 17 ), or triglucosides ( 21 – 23 ). In keeping with earlier results, the use of THF as solvent led mostly to β-D -glucosides. The modest regioselectivity in the formation of the monoglucosides, glucosylated either at O? C(1) or O? C(10), is rationalized on the basis of the relative kinetic acidity of the intra- and intermolecularly H-bonded OH groups of 1b . The tertiary HO? C(3) of the monoglucosides was more readily glucosylated than the secondary HO? C(1) or HO? C(10) (H-bonded). Glucosidation with 3.5 equiv. of 2 led to triglucosides, with the tri-β-D -glucoside 21 (42%) as the major product. Catalytic hydrogenation afforded the free glucosides 9 – 12 , 18 – 20 , and 24 . The di- and triglucosides are readily soluble in H2O. Glucosidation with 2 of the ginkgolide-A-derived tertiary alcohol 25 yielded 93% of the β-D -anomeric glucoside 26 . Similarly, glycosidation of 25 with the lactosylidene-derived diazirine 34 proceeded with a very high stereoselectivity, yielding 92% of the β-D -lactoside 35 , that was deprotected to the H2O soluble acetate 36 .  相似文献   

11.
The N′-(glycofuranosylidene)toluene-4-sulfonohydrazides 5 and 10 (Scheme 1) were prepared in good yields by oxidation (1,3-dibromo-5,5-dimethylhydantoin/Et3N) of the N′-glycosyltoluene-4-sulfonohydrazides 4 and 9 , which were obtained from 2,3,5-tri-O-benzyl-D -ribose ( 3 ) and 2,3,5-tri-O-benzyl-D -arabinose ( 8 ), respectively, and toluene-4-sulfonohydrazide. The analogous naphthalene-2-sulfonohydrazides 7 and 12 were similarly prepared from 3 and 8 via 6 and 11 . Photolysis in the presence of phenol of the sodium salt 15 (Scheme 2), best generated in situ, yielded the anomeric glycosides 16 , some 5 , and traces of the glycosides (1R)/(1S)- 17 . Photolysis of 15 in THF gave the sulfones α-D /β-D - 18 . Photolysis of 15 (quartz filter) and dimethyl fumarate led to a single cyclopropane 19 , the sulfones α-D /β-D - 18 , and the N-(ribofuranosyl)-N′-(ribofuranosylidene)toluene-4-sulfonohydrazide 20 . Similarly, N-phenylmaleimide afforded the cyclopropanes 21 and 22 . Photolysis of the sodium salt of 10 and phenol afforded the anomeric glycosides α-D /β-D - 23 , the C-glycoside 24 , and the sulfone 25 . Photolytic glycosidation of 15 with N6-benzyladenine gave the two nucleosides 26 and 27 (Scheme 3).  相似文献   

12.
The regio- and stereoselectivity of the glycosidation of the partially protected mono-alcohols 3 and 7 , the diols 2 and 8 , and the triol 4 by the diazirine 1 have been investigated. Glycosidation of the α-D -diol 2 (Scheme 2) gave regioselectively the 1,3-linked disaccharides 11 and 12 (80%, α-D /β-D 9:1), whereas the analogous reaction with the βD -anomer 8 led to a mixture of the anomeric 1,3- and 1,4-linked disaccharides 13 (12.5%), 14 (16%), 15 (13%), and 16 (20.5%; Table 2). Protonation of the carbene by OH–C(4) of 2 is evidenced by the observation that the α-D -mono-alcohol 3 did not react with 1 under otherwise identical conditions, and that the β-D -alcohol 7 yielded predominantly the β-D -glucoside 18 (52%) besides 14% of 17 . Similarly as for the glycosidation of the diol 2 , the influence of the H-bond of HO? C(4) on the direction of approach of the carbene, the role of HO? C(4) in protonating the carbene, and the stereoelectronic control in the interception of the ensuring oxycarbenium cation are evidenced by the reaction of the triol 4 with 1 (Scheme 3), leading mostly to the α-D -configurated 1,3-linked disaccharide 19 (41%), besides its anomer 20 (16%), and some 4-substituted β-D -glucoside 21 (9%). No 1,6-linked disaccharides could be detected. In agreement with the observed reactivity, the 1H-NMR and IR spectra reveal a strong H-bond between HO? C(3) and the phthalimido group in the α-D -, but not in the β-D -allosides. The different H-bonds in the anomeric phthalimides are in keeping with the results of molecular-mechanics calculations.  相似文献   

13.
14.
To demonstrate the relevance of the kinetic acidity of individual OH groups for the regioselectivity of glycosylation by glycosylidene carbenes, we compared the glycosylation by 1 of the known triol 2 with the glycosylation of the diol D - 3 and the fluorodiol L - 4 . Deoxygenation with Bu3SnH of the phenoxythiocarbonyl derivative of 5 (Scheme 1) or the carbonothioate 6 gave the racemic alcohol (±)- 7 . The enantiomers were separated via the allophanates 9a and 9b , and desilylated to the deoxydiols D - and L - 3 , respectively. The assignment of their absolute configuration is based upon the CD spectra of the bis(4-bromobenzoates) D - and L - 10 . The (+)-(R)-1-phenylethylcarbamates 13a and 13b (Scheme 2) were prepared from the fluoroinositol (±)- 11 via (±)- 4 and the silyl ether (±)- 12 and separated by chromatography. The absolute configuration of 13a was established by X-ray analysis. Decarbamoylation of 13a ( → L - 12 ) and desilylation afforded the fluorodiol L - 4 . The H-bonds of D - 3 and L - 4 in chlorinated solvents and in dioxane were studied by IR and 1H-NMR spectroscopy (Fig. 2). In both diols, HO? C(2) forms an intramolecular, bifurcated H-bond. There is an intramolecular H-bond between HO? C(6) and F in solutions of L - 4 in CH2Cl2, but not in 1,4-dioxane; the solubility of L - 4 in CH2Cl2 is too low to permit a meaningful glycosidation in this solvent. Glycosidation of D - 3 in dioxane by the carbene derived from 1 (Scheme 3) followed by acetylation gave predominantly the pseudodisaccharides 18/19 (38%), derived from glycosidation of the axial OH group besides the pseudodisaccharides 16 / 17 (13%) and the epoxides 20 / 21 (7%), derived from protonation of the carbene by the equatorial OH group. Similarly, the reaction of L - 4 with 1 (Scheme 4) led to the pseudodisaccharides 28 / 29 (46%) and 26 / 27 (14%), derived from deprotonation of the axial and equatorial OH groups, respectively. Formation of the epoxides involved deprotonation of the intramolecularly H-bonded tautomer, followed by intramolecular alkylation, elimination, and substitution (Scheme 4). The regio- and diastereoselectivities of the glycosidation correlate with the H-bonds in the starting diols.  相似文献   

15.
Glycosylidene carbenes derived from the GlcNAc and AllNAc diazirines 1 and 3 were generated by the thermolysis or photolysis of the diazirines. The reaction of 1 with i-PrOH gave exclusively the isopropyl α-D -glycoside of 5 besides some dihydrooxazole 9 (Scheme 2). A similar reaction with (CF3)2CHOH yielded predominantly the α-D -anomer of 6 , while glycosidation of 4-nitrophenol (→ 7 ) proceeded with markedly lower diastereoselectivity. Similarly, the Allo-diazirine 3 gave the corresponding glycosides 12–14 , but with a lower preference for the α-D -anomers (Scheme 3). The reactions of the carbene derived from 1 with Ph3COH (→ 8 ) and diisopropylideneglucose 10 (→ 11 ) gave selectively the α-D -anomers (Scheme 2). The αD -selectivity increases with increasing basicity (decreasing acidity) of the alcohols. It is rationalized by an intermolecular H-bond between the acetamido group and the glycosyl acceptor. This H-bond increases the probability for the formation of a 1,2-cis-glycosidic C–O bond. The gluco-intermediates are more prone to forming a N–H…?(H)OR bond than the allo-isomers, since the acetamido group in the N-acetylallosamine derivatives forms an intramolecular H-bond to the cis-oriented benzyloxy group at C(3), as evidenced by δ/T and δ/c experiments.  相似文献   

16.
The diazirine 1 , upon thermolysis or photolysis in either acetone or cyclohexanone, at different concentrations, yield the spiro epoxides 2 and 3 , and 4 and 5 , respectively (Scheme 1). Yield of 2 and 3 depended both on the temperature and the concentration, and correlated inversely with the yield of the major by-product, the enol-derived glycoside 6 . Other by-product were the benzyloxglycal 7 and the lactone azines 8 . ZnCl2-Promoted methanolysis of 2 under mild condition yielded mixture of the uloside 9 and 10 (1.2:1); similarly, 4 yielded 11 and 12 (1.8:1; Scheme 2). More strongly acidic conditions converted 11 into 12 , evidencing that ZnCl2-promoted methanolysis proceeds under kinetic control, which is rationalized. The diazirine 13 , upon thermolysis of Photolysis in either acetone of cyclohexanone, yielded the α-D -configurated spiro epoxides 14 and 16 , and the α-D -configurated dihydrooxazoles 15 and 17 , respectively (Scheme 3), which are either formed by ring-opening of ß-D -epoxides, by competitive interception of the initially formed, hypothetical addition products of the intermediate carbene to the ketones. The glycosylidene carbenes, derived from 1 or 13 are not very reactive towards ketones, yields are good only when sterically unhindered ketones are used in large excess.  相似文献   

17.
Hydrogen bonding of the triol 4 in chlorinated solvents was studied by IR (CH2Cl2 and CCl4) and 1H-NMR spectroscopy (CDCl3), and the regioselectivity of the glycosidation of the triol 4 by the diazirine 1 is predicted on the basis of two assumptions: preferred protonation of the intermediate glycosylidene carbene by the OH group involved in the weakest intramolecular H-bond, and attack in the π-plane of the thereby generated oxycarbenium cation either by the reoriented oxy anion, or by a properly oriented vicinal OH group. Glycosidation led to the disaccharides 5–10 (Scheme) which were separated and characterized as their acetates 11–16 , to the lactone azines 17 and to the 2-(benzyloxy)glucal 18 . In agreement with the predictions, glycosidation in non-coordinating solvents gave the 1,2-, 1,3-, and 1,4-linked disaccharides in decreasing relative amounts. Glycosidation in THF proceeded with a lower degree of regioselectivity and led preferentially to the β -D -anomers, except for the minor, 1,4-linked disaccharides, where THF had only a weak influence on stereoselectivity at room temperature and led to a slight increase of the α -D -anomer at ?80°.  相似文献   

18.
The relation between H-bonding in diequatorial trans-1,2 and axial, equatorial cis-1,2-diols and the regioselectivity of glycosidation by the diazirine 1 was examined. H-Bonds were assigned on the basis of FT-IR and 1H-NMR spectra (Fig. 1). Glycosidation by 1 of the gluco-configurated diequatorial trans-2,3-diols 4–7 yielded the mono-glucosylated products 16/17/20/21 (69–89%); 1,2-/1,3-linked products (37–46:63–54), 24/25/28/29 (60–63%; 1,2-/1,3-linked products 46–51:54–49), 32–35 (69–94%; 1,2-/1,3-linked products 45–52:55–48), and 36/37/40/41 (59–63%; 1,2-/1,3-linked products 52–59:48–41), respectively (Scheme 1, Table 3). The disaccharides derived from 4, 5 , and 7 were characterized as their acetates 18/19/22/23, 26/27/30/31 , and 38/39/42/43 , respectively. Glycosidation of the galacto-configurated diequatorial 2,3-diols 8 and 9 and the manno-configurated diequatorial 3,4-diol 10 by 1 (Scheme 2, Table 3) also proceeded in fair yields to give the disaccharides 44–47 (69–80%;1,2-/1,3-linked products ca. 1:1), 48–51 (51–61%;1,2/-1,3-linked products 54–56:56–54), and 56/57/60/61 (71–80%; 1,3-/1,4-linked products 49–54:51–46), respectively. The 1,3-linked disaccharides 56/57 derived from the diol 10 were characterized as the acetates 58/59 . The regio- and stereoselectivities of the glycosidation by 1 were much better for the α-D -manno-configurated axial, equatorial cis-2,3-diol 11 and the galacto-configurated axial, equatorial cis-3,4-diol 13 (1,2-/1,3-linked disaccharides ca. 3:7 for 11 and 1,3-/1,4-linked disaccharides ca. 4:1 for 13 ; Scheme 3, Table 4). The regio- and stereoselectivity for the β-D -manno-configurated cis-2,3-diol 12 were, however, rather poor (1,2-/1,3-linked products 48:52). The 1,2-linked disaccharides 66/67 derived from 12 were characterized as the acetates 70/71 . Koenigs-Knorr-type glycosidation of the cis-diols 11–13 by 2 or 3 proceeded with a similar regio- and a higher stereoselectivity (α-D > β-D with the donor 2 and α-D < β-D with the donor 3 ) than with 1 , with the exception of 12 which did not react with 2 . The regioselectivity of the glycosidations by 1 agrees fully with the H-bonding scheme of the diols and with the hypothesis that the intermediate carbene is preferentially protonated by the most weakly H-bonded OH group. The regioselectivity of the glycosidation by 2 and by 3 is determined by a higher reactivity of the equatorial OH groups and by H-bonding. Several H-bonded and equilibrating isomers of a given diol may intervene in the glycosidation by 1 , or by 2 and 3 , resulting in the same regioselectivity. The low nucleophilicity of 12 and the low degree of regioselectivity in its reaction with 3 show that stereoelectronic effects may also profoundly influence the nucleophilicity of OH groups.  相似文献   

19.
Glycosidation of the myo-inositol derivatives 2 and 3 by the diazirine 1 yields 90% of a diastereoisomer pair of β-D -glycosides in a 1:1 ratio, i.e. 5/6 and 7/8 , respectively (Scheme 1). The crystal structure of 3 shows a strong intramolecular H-bond, which persists in solution, as indicated by FT-IR and 1H-NMR spectra. Yields and diastereoselectivity are lower for the glycosidation of 24 by 1 (Scheme 3). The resulting 1,2- and 1,4-linked disaccharides 25–28 were isolated as their acetates 29–32 . The previously determined crystal structure of 24 shows no intramolecular H-bonds. The yield of the glycosidation of 24 , but not of 3 , depends upon the concentration, indicating that activation of 24 by intermolecular H-bonds is required. Glycosidation of 2 and 3 with the trichloroacetimidate 14 gave mixtures of four ( 5,6,15 , and 16 ), and six ( 7,8 , and 17–20 ) disaccharides, respectively (Scheme 2).  相似文献   

20.
A new approach towards the synthesis of glycosides based upon a (formal) insertion of glycosylidene carbenes into O? H bonds is presented. The synthesis and characterization of the glycosylidene-derived diazirines 25 – 28 , precursors of glycosylidene carbenes, are described. The diazirines were prepared by the rapid, high-yielding oxidation of the diaziridines 20 and 22 – 24 with I2/Et3N. The diaziridines, the first examples of C- alkoxy-diaziridines, were formed in high yields by the reaction of the [(glycosylidene)-amino]methanesulfonates 14 and 17 – 19 with a saturated solution of NH3 in MeOH. The diazirines are highly reactive compounds, losing N2 at room temperature or below. The reaction of the gluco-configurated diazirine 25 with i-PrOH yielding a mixture of the α- and β-D -glucosides 29 and 30 illustrates the potential of glycosylidene-derived diazirines as a new type of glycosyl donors.  相似文献   

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