Synthesis of carbohydrate

1.13 Synthesis of Monosaccharides and Analogs P Vogel, Ecole Polytechnique Fe´de´rale de Lausanne, Lausanne, Switzerland I Robina, Universidad de Sevilla, Seville, Spain ß 2007 Elsevier Ltd All rights reserved 1.13.1 Introduction 490 1.13.2 The Formose Reaction 490 1.13.3 Prebiotic Synthesis of Carbohydrates 491 1.13.4 Aldolase-Catalyzed Asymmetric Aldol Condensations 493 1.13.4.1 Resolution of Racemic Aldehydes 494 1.13.4.2 One-Pot Total Syntheses of Carbohydrates 496 1.13.4.3 Synthesis of 1,5-Dideoxy-1,5-Iminoalditols 497 1.13.4.4 Synthesis of 2,5-Dideoxy-2,5-Iminoalditols 498 1.13.4.5 Synthesis of Deoxythiohexoses 498 1.13.4.5.1 Use of aldolase antibodies 500 1.13.5 Asymmetric Synthesis of Carbohydrates Applying Organocatalysis 501 1.13.5.1 Synthesis of Ketoses 502 1.13.5.2 Synthesis of Aldoses 503 1.13.5.3 Synthesis of Amino Sugars by Aldol and Mannich Reactions 506 1.13.6 Chain Elongation of Aldehydes through Nucleophilic Additions 507 1.13.6.1 Total Synthesis of D- and L-Glyceraldehyde and Other C3 Aldose Derivatives 508 1.13.6.2 One-Carbon Homologation of Aldoses: The Thiazole-Based Method 512 1.13.6.3 Other Methods of One-Carbon Chain Elongation of Aldoses 513 1.13.6.4 Additions of Enantiomerically Pure One-Carbon Synthon 515 1.13.6.5 Two-Carbon Chain Elongation of Aldehydes 515 1.13.6.5.1 1.13.6.5.2 1.13.6.5.3 1.13.6.5.4 1.13.6.5.5 1.13.6.5.6 1.13.6.5.7 1.13.6.5.8 Asymmetric aldol reactions Nucleophilic additions to enantiomerically pure aldehydes Nitro-aldol condensations Nucleophilic additions of enantiomerically pure enolates Aldehyde olefination and asymmetric epoxidation Aldehyde olefination and dihydroxylation Aldehyde olefination and conjugate addition Allylation and subsequent ozonolysis 1.13.6.6 Three-Carbon Chain Elongation 1.13.6.6.1 1.13.6.6.2 1.13.6.6.3 1.13.6.6.4 529 Allylmetal additions Wittig–Horner–Emmons olefination Aldol reaction Other methods of three-carbon chain elongation of aldoses and derivatives 1.13.6.7 Four-Carbon Chain Elongation 1.13.6.7.1 1.13.6.7.2 1.13.6.7.3 515 516 519 519 522 523 527 527 529 531 531 531 532 (But-2-en-1-yl) metal addition Nucleophilic addition of a-furyl derivatives Hydroxyalkylation of pyrrole derivatives 1.13.6.8 Synthesis of Branched-Chain Monosaccharides from C3-Aldoses 532 533 534 534 1.13.7 Hetero-Diels–Alder Additions 536 1.13.7.1 Achiral Aldehydes as Dienophiles 536 1.13.7.2 Chiral Aldehydes as Dienophiles: Synthesis of Long-Chain Sugars 537 1.13.7.3 Hetero-Diels–Alder Addition of 1-Oxa-1,3-Dienes 540 489 490 Synthesis of Monosaccharides and Analogs 1.13.7.3.1 1.13.7.3.2 1.13.7.3.3 1.13.7.4 1.13.7.5 1.13.8 With chiral 1-oxa-1,3-dienes With chiral enol ethers as dienophiles Induced asymmetry by the Lewis acid catalyst 540 541 542 Nitroso Dienophiles: Synthesis of Azasugars 544 N-Methyltriazoline-3,5-Dione as Dienophile: Synthesis of 1-Azafagomine 545 Cycloadditions of Furans 546 1.13.8.1 Diels–Alder Additions 546 1.13.8.2 The ‘Naked Sugars of the First Generation’ 547 1.13.8.2.1 1.13.8.2.2 1.13.8.2.3 1.13.8.2.4 1.13.8.2.5 1.13.8.3 1.13.8.4 1.13.9 Total synthesis of pentoses and hexoses Total syntheses of deoxyhexoses Total synthesis of aminodeoxyhexoses and derivatives Long-chain carbohydrates and analogs ‘Naked sugars of the second generation’: Synthesis of doubly branched-chain sugars 547 548 551 553 555 Dipolar Cycloadditions of Furan 555 [4ỵ3]-Cycloadditions of Furan 556 Carbohydrates and Analogs from Achiral Polyenes 559 1.13.9.1 From Cyclopentadiene 559 1.13.9.2 From Benzene and Derivatives 561 1.13.9.3 From Cycloheptatriene 561 1.13.9.4 From Penta-1,4-Diene 563 1.13.9.5 From Furfural 563 1.13.10 Enantioselective Epoxidation of Allylic Alcohols 564 1.13.10.1 Desymmetrization of meso-Dienols 565 1.13.10.2 Kinetic Resolution of Racemic Allylic Alcohols 567 1.13.11 Enantioselective Sharpless Dihydroxylation and Aminohydroxylation 568 1.13.12 Conclusion 573 1.13.1 Introduction Total synthesis of carbohydrates and analogs has kept chemists busy since 1861 when Butlerow1a–1e discovered the ‘formose reaction’, which generates mixtures of racemic aldoses and ketoses by oligomerization of formaldehyde in the presence of Ca(OH)2 Nowadays, with the advent of highly stereoselective and enantioselective methods, almost any natural or non-natural carbohydrates can be obtained readily from inexpensive starting materials in enantiomerically pure form D-Glucose, D-mannose, D-glucosamine, D- and L-arabinose of natural source are certainly cheaper than from total synthesis But when it deals with unnatural enantiomers of common carbohydrates, or with unusual derivatives in which hydroxy groups are replaced by amino moieties, by alkoxy groups, thio, halogeno, carbon substituents, etc., total synthesis from non-carbohydrate precursors may be easy and advantageous By total synthesis, the carbohydrates are delivered in suitably protected forms In contrast, by starting from natural sugars, this sometimes requires several delicate chemical operations This chapter describes the most important synthetic approaches that have been developed during the last 25 years It will concentrate on techniques generating enantiomerically enriched, or pure carbohydrates and analogs For earlier work, the reader will have to consult available reviews.2a–3b Aldoses, alditols, and their derivatives will be considered, including aza and thiosugars (with nitrogen and sulfur in the pyranose or furanose rings) 1.13.2 The Formose Reaction The formose reaction has been developed by Loew4a,4b and Fischer,5a,5b who isolated rac-fructose osazone from the formose reaction mixture The reaction shows an induction period during which small amounts of glycolaldehyde, glyceraldehyde, and dihydroxyacetone are formed, which are believed to act as catalytic species by complexing with Synthesis of Monosaccharides and Analogs i, Et3N, DMF/H2O 6CH2O OAc ii, Ac2O, pyr HO O Thiamine⋅HCl N NH2 S OAc OAc OAc ⋅HCl N N 491 OH Cl 28% Thiamine⋅HCl Scheme Examples of selective formose reaction S H S Base N − +HCHO N + S +HCHO H N H + S N + − N + S OH − O N + H + S H O H − S H OH OH N + O H +HCHO OH O OH DHA Scheme Possible mechanism for the DHA synthesis calcium ions, in the subsequent steps The yield of formose sugars reaches a maximum at the so-called yellowing point.6 On further reaction, branched sugars are formed involving aldol condensations followed by cross-Cannizarro reactions.7 Depending on the nature of the base and additives used to induce the formaldehyde oligomerization, various proportions of trioses, tetroses, pentoses, hexoses, and long-chain aldoses and ketoses are obtained.8a–8c The addition of glycoaldehyde or a higher aldose to the reaction mixture reduces considerably the induction period for the oligomerization Umpolung catalysts of the thiamin type also reduce the induction period.9a–9c When carried out in dimethylformamide (DMF¼N, N-dimethylformamide), considerable control in the product distribution of the formose reaction is possible by adjustment of the water content (Scheme 1) When, for instance, formaldehyde is heated to 75  C for 1h with Et3N and thiamin hydrochloride in 8:1 DMF/H2O, DL-2-C-hydroxymethyl-3-pentulose, characterized as its tetraacetate 1, is produced in 28% yield.10 The formose reaction has been investigated using immobilized thiazolium catalyst.11 Under these conditions, the main products are dihydroxyacetone (DHA), erythrulose, and 4-hydroxymethyl-2-pentulose The relative importance of these products depends on the amount of thiazolium salts and concentration in 1,4-dioxane.12–14 A possible mechanism for the formation of dihydroxyacetone is shown in Scheme (Stetter reaction15a–15d analogous to the benzoin condensation catalyzed by cyanide anion) Eschenmoser and co-workers16a,16b studied the aldomerization of glycolaldehyde phosphate which led to mixtures containing mostly racemates of the two diastereomeric tetrose 2,4-diphosphates and eight hexose 2,4,6-triphosphates (Scheme 3, route A) At 20  C in the absence of air, a 0.08 molar solution of glycolaldehyde phosphate in M NaOH gave 80% yield of a 1:10 mixture of tetrose and hexose derivatives with DL-allose 2,4,6-triphosphate comprising up to 50% of the mixture of sugar phosphate In the presence of formaldehyde (0.5mol equiv.), sugar phosphates were formed in up to 45% yield, with pentose 2,4-diphosphates dominating over hexose triphosphates by a ratio of 3:1 (Scheme 3, route B) The major component was found to be DL-ribose 2,4-diphosphate, the ratios of ribose, arabinose, lyxose, and xylose 2,4-diphosphate being 52:14:23:11 The aldomerization of in the presence of H2CO is a variant of the formose reaction It avoids the formation of complex product mixtures as a consequence of the fact that aldoses which are phosphorylated at the C(2) position cannot undergo aldose–ketose tautomerization The preference for ribose 2,4-diphosphate and allose 2,4,6-triphosphate formation might have significance to the discussion about the origin of ribonucleic acids 492 Synthesis of Monosaccharides and Analogs OPO3Na2 O OH CHO CHO OPO3Na2 NaOH H2O OPO3Na2 OH OPO3Na2 H2O (a) CHO NaOH OPO3Na2 + CH2O NaOH H2O Na2O3PO HO OPO3Na2 CHO OH OPO3Na2 + Hexose 2,4,6-triphosphates OH OPO3Na2 major (b) Scheme a, Selective condensation of glycolaldehyde phosphate alone; b, in the presence of formaldehyde CH2O + CO + H2 Cat 2CH2O + CO + H2 Cat 2CH2O + 2CO + H2 Cat C4H8O4 3CH2O + 2CO + 2H2 Cat C5H10O5 3CH2O + 3CO + 3H2 Cat HOCH2CHO C3H6O3 Cat.: Rh(CO)(Ph3P)2Cl and tertiary amines C6H12O6 Scheme Rh(I)-catalyzed condensations of formaldehyde with syn-gas giving linear carbohydrates The ‘classical’ formose reaction gives a very large number of carbohydrates including branched-chain isomers.8a–8c Straight-chain carbohydrates such as trioses, tetroses, pentoses, and hexoses are readily obtained in good yield by a reaction of formaldehyde with syngas in the presence of RhCl(CO)(PPh3)2 and tertiary amines (Scheme 4).17 1.13.3 Prebiotic Synthesis of Carbohydrates The formation of Earth from a diffuse cloud of cosmic gas and dust occurred some 4.6Â109 years ago It is proposed that c 4.0Â109 years ago bodies of water were formed and organic chemistry became established The oldest known fossils date back to c 3.6Â109 years and show resemblance to modern blue green algae Biogenesis from organic chemistry to a primitive cell must therefore have occurred in the time in-between of c 0.4Â109 years It is accepted that there was no free oxygen until the advent of photosynthetic bacteria c 2.7Â109 years ago Under these (reductive) conditions, energy required for chemical synthesis would be available from the sun in the form of ultraviolet radiation, blocked today by the ozone layer Water, ammonia, HCN, acetonitrile, acrylonitrile, cyanogen, cyanoacetylene, and formaldehyde are believed to be the building blocks for nature Laboratory experiments have shown that HCN is formed in good yield from gaseous mixtures of N2, H2, and NH3 in spark discharge experiments of by the action of ultraviolet radiation on mixtures of CH4 and NH3, gases abundant in outer space A spark discharge passed through CH4 and N2, or through HCN, produced cyanoacetylene and cyanogen, respectively Similar experiments have demonstrated the formation of formaldehyde.18 Shevlin and co-workers19 have reported that co-condensation of carbon with H2O and NH3 at 77K generates amino acids They also showed that atomic carbon generated by vaporizing in an arc under high pressure reacts with water at 77K to form low yields of straight-chain aldoses with up to five carbon centers A mechanism (Scheme 5) involving hydroxymethylene species has been supported by deuterium labeling studies.20 Under UV irradiation, neutral aqueous solutions of formaldehyde form CO, CO2, CH4, CH3CH3, and ethylene gas At the same time, formaldehyde condenses into glycoaldehyde and glyceraldehyde, two active precurors in the formose reaction This might correspond to reactions that occurred on prebiotic Earth and that have led to the first carbohydrates via the formose reaction.21 There is a debate whether the ‘classical’ formose reaction 3a–5b might have played a role in the prebiotic synthesis of carbohydrates When slurry of carbonate-apatite is boiled with 0.5M formaldehyde at pH 8.5, a yield lower then Synthesis of Monosaccharides and Analogs O :C H HCOH H2C O H (D)H O H C OH 77 K C + H2O (D)HO H2C 77 K O HCOH H(D) H(D) HCOH Tetroses 493 HO OH O H2C C C H H Pentoses Scheme Reaction of carbon atoms with water: formation of aldoses O OH OH [Fe(OH)O] 15 ЊC, pH 5–6 O OH HO + OH OH (±)-Sorbose 15.2% Glyceraldehyde OH O OH Dihydroxyacetone HO HO OH + OH OH (±)-Fructose 12.9% O OH OH HO OH OH (±)-Psicose 6.1% OH O OH O OH HO + + HO HO OH HO COOH OH Me Lactic acid O HO (±)-Tagatose 5.6% CH2OH OH (±)-Dendroketose 2.5% Scheme [Fe(OH)O]-catalyzed reactions of D,L-glyceraldehyde O :S OH O−M+ O + RCHO S O− M + H O O H R Scheme Sulfite anion and aldehyde adduct formation: a possible concentration process in double-layer hydroxide minerals such as Mg2Al(OH)6ỵ[SO3H(H2O)2] 40% in sugars is reached after a few hours Prolonged heating decomposes the carbohydrates Sugars have been detected from 0.01M formaldehyde but not from 0.001 M solution Thus it appears than the ‘classical’ formose model for prebiotic accumulation of sugars is not plausible because it requires concentrated solutions of formaldehyde and the sugars formed are rapidly decomposed.22 Iron(III)hydroxide oxide [Fe(OH)O] has been shown to catalyze the condensation of 25mM DL-glyceraldehyde to ketohexoses at 15  C (pH 5–6) After 16 days, 15.2% of sorbose, 12.9% of fructose, 6.1% of psicose, 5.6% of tagatose, and 2.5% of dendroketose are obtained After 96 days at 15  C, this mixture was not decomposed [Fe(OH)O] also catalyzes the isomerization of glyceraldehyde into dihydroxyacetone and of dihydroxyacetone into lactic acid (Scheme 6).23 The ‘classical formose’ conditions are not capable to produce large amounts of ribose (for RNA synthesis), nor of any other individual sugar In contrast, the reduced sugar pentaerythritol is formed with great selectivity by the ultraviolet irradiation of 0.1M formaldehyde This compound may have played an important role in prebiotic chemistry.24 The seminal work of Eschenmoser and co-workers16a,16b (Scheme 3) suggests that the ‘initial RNA world’ might have involved glycoaldehyde phosphate.25 In order to explain the concentration process required, one can envisage that double-layer hydroxide minerals might have played a decisive role, in particular those incorporating sodium sulfite, which can absorb formaldehyde, glycoaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite anions This translates into observable uptake at concentration !50mM (Scheme 7).26 Sugars have been proposed to be the optimal biosynthetic carbon substrate of aqueous life throughout the universe.27 494 Synthesis of Monosaccharides and Analogs Benner and co-workers28 have followed the formation of pentoses under alkaline conditions from simple precursors such as formaldehyde and glycolaldehyde in the presence of borate minerals The latter stabilize the pentose selectively by forming complexes 1.13.4 Aldolase-Catalyzed Asymmetric Aldol Condensations The enzymatic aldol addition represents a useful method for the synthesis of various sugars and sugar-like structures.29a–29e More than 20 different aldolases have been isolated (see Table for examples) and several of these have been cloned and overexpressed.30 They catalyze the stereospecific aldol condensation of an aldehyde with a ketone donor Two types of aldolases are known Type I aldolases found primarily in animals and higher plants not require any cofactor The X-ray structure of the aldolase from rabbit muscle (RAMA¼rabbit muscle aldolase) indicate that Lys-229 is responsible for Schiff-base formation with dihydroxyacetone phosphate (DHAP) (Scheme 8a) Type II aldolases found primarily in microorganism use Znỵỵ as cofactor which acts as a Lewis acid enhancing the electrophilicity of the ketone (Scheme 8b) In both cases, the aldolases accept a variety of natural (Table 1) and of Table Examples of enzymes catalyzing the equilibria of natural products with various aldol donors and various aldehydes (the wavy line indicating the C–C bond involved in the reversible aldol reaction)29a–29e Aldol donor (nucleophiles) DHAP O OP − OH O OP − PO OH OOC OH OH O OOC OH OH FDP aldolase OH OH − OOC OP OH DAHP synthetase 3-Deoxy-2-oxo-6-Pgluconate aldolase O OH O − PO O OH O OOC OP OH Fuculose-1-P-aldolase OH OH O OH OH OH OH OH OH O OH AcNH Sialic acid synthetase O − OH OH OH AcNH OH Sialic acid aldolase O OH OP OH 3-Deoxy-2-oxo-6-PTagatose-1,6-P2 aldolase OH OH OH − OOC OH OH OOC OP PO OH Kdo aldolase − OOC OH OH OOC OH Kdo synthetase OH PO − OH galactonate aldolase 495 Synthesis of Monosaccharides and Analogs Table (continued) Aldol donor O − O OOC H O − OOC OH O OH O − OOC − COO OH OP H − OOC O HO Me O − COO NH3 OH 3-Deoxy-2-oxo-Larabinoate aldolase 2-Deoxyribose5-P-aldolase − OOC OH Me OH D-Thr OH − OOC NH3 − OOC OH 4-Hydroxy-2-oxoglutarate aldolase − OOC Me aldolase NH3 Me OH 4-Hydroxy-4-methyl-2oxoglutarate aldolase O OH − OOC 3-Deoxy-2-oxo-Dpentanoate aldolase L-Thr O − COO − OOC aldolase NH3 − OOC OH OH OH 3-Deoxy-2-oxo-Dglucarate aldolase O Hydroxybutyrate aldolase Ser-hydroxymethyl transferase HO HO HO OH OH − COO O − OOC OH OH OH N-Acetylneuraminic acid aldolase from E coli O OH (Kdo) OH OH − OOC OH OH OH − OOC OH OH OH − OOC O OH HO HO OH AcNH OH OH OH OH OH enantiomer of Kdo N-Acetylneuraminic acid aldolase mutant O HO − OOC O OH OH NHAc OH enantiomer of Neu5Ac N-Acetylneuraminic acid aldolase mutant33 FDP, fructose-1,6-diphosphate; DHAP, dihydroxyacetone phosphate; Kdo, 3-deoxy-D-manno-oct-2-ulosonate; P¼ 2–O3P non-natural acceptor substrates (Scheme 9) N-acetylneuraminic acid aldolase (Neu5Ac aldolase) from Escherichia coli catalyzes the reversible aldol reaction of N-acetyl-D-mannosamine and pyruvate to give N-acetylneuraminic acid (sialic acid) This enzyme is quite specific for pyruvate as the donor, but flexible to a variety of D- and, to some extent, 31a,31b L-hexoses and L-pentoses as acceptor substrates Using error-prone PCR (polymerase chain reaction) for in vitrodirected evolution, the Neu5Ac aldolase has been altered to improve its catalytic activity toward enantiomeric substrates such as N-acetyl-L-mannosamine and L-arabinose to produce the enantiomer of sialic acid (a potent 496 Synthesis of Monosaccharides and Analogs −− Lys-Enz HN O3PO −− OH H (a) H N OH OH O3PO R H (b) O O Zn Enz N ++ R Scheme a, Type I aldolases form enamine nucleophiles (donor); b, type II aldolases use Zn2ỵ as cofactor activating the aldehyde (acceptor) O R H OH O RAMA + DHAP R = H, Me, ClCH2, CHO, COOH, N3CH2CHO, THPOCH2, PhCOOCH2 O Y OH O −− OPO3 Y X X = H, Me, OH, OMe, OAc, NHAc Y = H, OH, OPO3 OH O3POCH2, RAMA + DHAP H −− OPO3 R X OH , F, N3 Scheme Examples of RAMA-catalyzed aldol condensations −− O O3PO O OH + DHAP −− H FDP aldolase OPO3 OH G3P −− O3PO O OH −− OPO3 OH OH FDP Scheme 10 Stereospecific FDPaldolase-catalyzed aldol reaction of DHAPỵG3P FDP neuraminidase inhibitor for the treatment of flu is derived from sialic acid),32 and 3-deoxy-L-manno-oct-2-ulosonic acid (the enantiomer of Kdo)30,33 (Table 1) 1.13.4.1 Resolution of Racemic Aldehydes Fructose-1,6-diphosphate (FDP) aldolase catalyzes the reversible aldol addition of DHAP and D-glyceraldehyde3-phosphate (G3P) to form D-fructose-1,6-diphosphate (FDP), for which Keq %104 M–1 in favor of FDP formation (Scheme 10) RAMA accepts a wide range of aldehyde acceptor substrates with DHAP as the donor to generate 3S,4S vicinal diols, stereospecifically (Scheme 9) The diastereoselectivity exhibited by FDP aldolase depends on reaction conditions Racemic mixture of non-natural aldehyde acceptors can be partially resolved only under conditions of kinetic control When six-membered hemiacetals can be formed, racemic mixtures of aldehydes can be resolved under conditions of thermodynamic control (Scheme 11) DL-Glyceraldehyde and 1,3-dihydroxyacetone are obtained from glycerol mild oxidation, for instance with hydrogen peroxide in the presence of ferrous salts as catalysts.34 Selective formation of trioses has been observed in the formose reaction when a-ketols bearing electron-withdrawing substituents were added to the reaction mixture.35 In the presence of thiazolium salts, selective conversion of formaldehyde into 1,3-dihydroxyacetone has been reported.36a,36b Hydration of halopropargyl alcohol followed by hydrolysis gives 1,3-dihydroxyacetone.37a,37b DHAP can be generated by three different procedures: (1) in situ from fructose 1,6-diphosphate with the enzyme triosephosphate isomerase; (2) from the dimer of dihydroxyacetone by chemical phosphorylation with POCl3 (Scheme 12); or (3) from dihydroxyacetone by enzymatic phosphorylation using ATP and glycerol kinase, with in situ generation of the ATP using phosphoenol pyruvate (PEP) or acetyl phosphate as the phosphate donor (Scheme 13).34 Synthesis of Monosaccharides and Analogs O DHAP + OH H O DHAP + Me 497 −− P = P(O)O2 H OH OH O Me Me OP O + OH HO OH OH OP O OH HO >97% OH OP OH O + HO 97% 90% ee) OH i, NH3, MeOH, 100 8C ii, BzCl, K2CO3 OH OH OH i, TsO− ii, OMe OMe TsOH iii, NaN3 iv, LiAlH4, Et2O v, TsOH, H2O HO 3-epi-Daunosamine (L-xylo) Scheme 139 Total syntheses of 3-amino-2,3,6-trideoxyhexoses OH HO NH2 L-Daunosamine NH2 OH OH Synthesis of Monosaccharides and Analogs OH OTBS OTBS HO i, AD-mix-b ii, TBSCl, py i, SOCl2 ii, RuCl3 OH OBn 569 O O Bu4NF S O O OBn OBn TBS = SiMe2(t-Bu) SPh O PhSNa HO OSO3− OH OBn O i, mCPBA ii, AcONa, Ac2O OBn HO H OH OBn OH AD-mix-b, 25 ЊC, 2d t-BuOH/H2O (1:1) 96%, 82% ee OH OH O O Pd(OH)2, H2 (50 psi) MeOH, pH 1.0, 65 ЊC H OH 4-Deoxy-D-threose O O O AD-mix-a, 25 ЊC, d t-BuOH/H2O (1:1) 100%, 79% ee OH OH OH O O Pd(OH)2, H2 (50 psi) MeOH, pH 1.0, 65 ЊC H OH 4-Deoxy-L-threose O Scheme 140 Total asymmetric synthesis of tetritol and tetrose derivatives O AD-mix-a MeSO2NH2 aq t-BuOH ЊC OH O HO OH O OH mCPBA CH2Cl2 TsOH PhH, 80 ЊC O (+)-555 H2O2 NaOH O O O O (+)-Isolevo glucosenone O O O O H2NNH2⋅H2O AcOH (cat) MeOH, ЊC O OH MnO2 CH2Cl2 20 ЊC O O O (−)-Levoglucosenone O AD-mix-b MeSO2NH2 aq t-BuOH ЊC OH HO O O O O O O (−)-Isolevoglucosenone O (+)-Levoglucosenone Scheme 141 Total synthesis of (ỵ)- and ()-isolevoglucosenone and of (ỵ)- and ()-levoglucosenone Applying the same route, D- and L-mannose have been obtained in five-step synthesis (39% overall yield) from furfural Similarly, the same methodology has been extended to the preparation of D- and L-gulose and D- and L-talose (19% yield),300a,300b and to the synthesis of 2-deoxy- and 2,3-dideoxyhexoses.301 A route to difluorosugar 561 has been developed It includes a Stille coupling302a–302c of 556 and 557 that generates diene 558 Sharpless asymmetric dihydroxylation of 558 was chemoselective and provided diol 559 in 54% yield The corresponding acetonide 560 was then debenzylated with H2O2/LiOH After treatment with 12 M HCl in THF, the semiprotected 1-deoxy-1,1-difluoro-D-xylulose 562 was obtained (Scheme 142).303 570 Synthesis of Monosaccharides and Analogs Pd(OAc)2, CuI Ph3P, DMF OPMBz 30−40 ЊC 41% 557 MEM = MeOCH2CH2OCH2 PMBz = 4-MeOC6H4CO OMEM F + SnBu3 I F 556 (AD-mix-a) K2OsO4⋅2H2O (DHQD)2PHAL K3Fe(CN)6, K2CO3 t-BuOH/H2O 54% MEMO F F OMEM F F 558 MEMO F OH Acetone, CuSO4 TsOH, 20 ЊC 68% OPMBz OH OPMBz F OPMBz OH 560: R = PMBz 561: R = H 559 H2O2, LiOH CF2H O O i, HCl, THF ii, Acetone, TsOH, CuSO4 OH O HO 562 Scheme 142 Synthesis of 1-deoxy-1,1-difluoro-D-xylose O O R EtO i, NMO, OsO4 t-BuOH/acetone ii, Ac2O/py OH AD-mix-a R EtO OH 565 (80%, 80% ee) 566 (89%, 89% ee) 563: R = H 564: R = OBn O O OAc OH R EtO 566 OAc OH 567 55%, d.r 6:1 568 89%, d.r 5:1) O O HO OBn 569 d.r 5:1 O EtOOCCH2P(OCH2CF3)2 t-BuOK 18-crown-6 THF OBn O i, AD-mix-a 70% ii, t-BuMe2SiCl imidazole 80% HO HO + H i, NMO, OsO4 t-BuOH/acetone ii, TsOH/py 53% O OBn TBSO 571 NMO OsO4 MeOH 70% OBn O OEt 570 O HO O Bu4NF THF 80% O HO TBSO 572 d.r 10:1 HO O HO OBn HO OBn 573 91%, ee Scheme 143 O’Doherty’s iterative dihydroxylation of dienoates Ethyl D-galactonates 567 and 568 have been prepared by two successive dihydroxylations of dienoates 563 and 564, respectively (Scheme 143) Intermediate diol 566 has been converted into L-galacto-g-lactone 569 (Scheme 143).304 When using the (2Z,4E)-dienoate 570, the same sequence of dihydroxylations provided L-talo-glactone derivative 573.305 Both cis-((Ỉ)-576) and trans-2-substituted-1,2,3,6-tetrahydropyridin-3-ol (Ỉ)-577 have been prepared via an aldol condensation of tosylamide 574 with acrolein and subsequent ring-closing metathesis catalyzed by Grubbs’ I catalyst (Scheme 144).306 Asymmetric dihydroxylation of trans-acetonide (Ỉ)-577 with the Hsung–Vedejs AD-mix-b307 gave Synthesis of Monosaccharides and Analogs Ts N Ts H N COOEt i, (i-Pr)2NLi THF ii, Acrolein THF, 87% COOEt i, LiAlH4 THF, 87% ii, Me2C(OMe)2 p - TsOH, PhH 55% OH 574 Ts N Ts N Grubbs' cat I CH2Cl2 87−90% O O Ts N Hsung−Vedejs AD-mix-a 28 h O O O (±)-576 575 (±)-577 Ts N + O O (±)-577 Ts N HO OH (+)-578 42% O OH (−)-579 35% i, Red-Al, THF toluene 110 ЊC, h ii, MeOH/HCl 40% H N HO O + O HO 571 46% H N OH HO OH OH (+)-580 OH OH OH (+)-581 Hsung−Vedejs AD-mix-a : 1:3:3:2:0.1:0.05 alkene/K3Fe(CN)6/K2CO3/MeSO2NH2/(DHQ)2PHAL/OsO4 Grubbs’ cat I: (Cy3P)2Ru(Cl)2CHPh Scheme 144 Ring-closing metathesis and asymmetric dihydroxylation: synthesis of iminoalditols OEt O (HJQ)2PHAL(1.2 mol%) t-BuOH 582 OH 583 O CbzN H OH (EtO)3CH TsOH EtO + O i, NaIO4 ii, NaBH4 iii, TBSCl COOEt OH 584 583 7:1 O OTBS O CbzN H 585 O OH O COOEt CbzN H Bn OC NCl ONa OsO4 (1 mol%) O (i-Bu)2AlH 91% OH − mCPBA CH2Cl2 ЊC HO N Cbz OTBS 586 OH i, NaBH4,CeCl3 ii, OsO4/NMO N Cbz OTBS HO EtO OH OH N Cbz OTBS H2/Pd−C TsOH, MeOH HO OH H TSO N H OH − Scheme 145 Application of the Sharpless asymmetric aminohydroxylation and of the aza-Achmatowicz reaction to the synthesis of D-1-deoxymannonojirimycin 572 Synthesis of Monosaccharides and Analogs COOEt AD-mix-a CH3SO2NH2 t-BuOH/H2O ЊC 86% OH COOEt OH TBSCl/Et3N DMAP CH2Cl2 20 ЊC 64% 587 i, 4-NO2C6H4COCl py, DMAP, ЊC ii, NaN3/DMF 20 ЊC 80% COOEt N3 589 i, CF3COOH, THF/H2O, 20 ЊC ii, (i - Bu)2AlH, THF/acetone, −78 ЊC iii, TsOH/py (MeO)3CH/MeOH Me O TsHN (−)-591 OMe COOEt OH 588 93% ee OTBS i, H2/Pd−C EtOAc, 20 ЊC ii, TsCl, Na2CO3 Toluene/H2O 20 ЊC 80% OTBS OTBS COOEt NHTs 590 TBS = SiMe2 (t-Bu) T = 4-MeC6H4SO2 DMAP = 4-Me2NC5H4N COOEt 587 TsN=C=O Pd(Ph3P)4 THF, 86 % NTs O O O i, H2/Pd−C, EtOAc, 20 ЊC ii, NaOH/MeOH iii, CF3COOH/THF, 72% 592 ii, TsOH/py, (MeO)3CH, MeOH, 94% NHTs 593 TsHN i, (i-Bu)2AlH, THF/toluene, −78ЊC O Me O 594 OMe Scheme 146 New route to deoxyamino sugars (ỵ)-578 and ()-579 in 42% and 35% yield, respectively The tosyl groups and acetonides were then removed by RedAl and HCl/MeOH to give 1,5-dideoxy-1,5-imino-D-allitol (ỵ)-580 and 1,5-dideoxy-1,5-imino-L-mannitol (ỵ)-581 Similarly, reaction of trans-acetonide 577 with HsungVedejs AD-mix-a afforded acetonides ()-578 and (ỵ)-579 in 50 and 40% yield, respectively The latter were converted, as before, into 1,5-dideoxy-1,5-imino-L-allitol (À)-580 and 1,5-dideoxy-1,4-imino-D-mannitol (À)-581.307 The Sharpless asymmetric aminohydroxylation308 of the electron-deficient 2-vinylfuran 582 gives a 7:1 mixture of semiprotected amino alcohols 583 and 584 (41%) The major product 583 (>86% ee) was reduced by diisobutylaluminum hydride giving diol 585,300a,300b which can be converted into the b-hydroxyfurylamine derivative 586, an important synthetic building block for various biologically important compounds, including 1,5-dideoxy-1,5-iminoalditols (Scheme 145) A less regioselective, but shorter, way to intermediate 586 is the direct asymmetric aminohydroxylation of vinylfuran.310a–312b Sharpless asymmetric dihydroxylation of ethyl sorbate gives diol 587 regioselectively Selective silylation of 587 provided alcohol 588 (93% ee), which was esterified as a paranitrobenzoate and displaced with NaN3 to give the allylic azide 589 Hydrogenolysis of 589 and subsequent formation of a tosylamide furnished 590, which was then converted into methyl N-tosyl-a-D-tolyposaminide (À)-591 Alternatively, diol 587 was reacted with TsN¼C¼O to give 592 (Ts ¼ para-toluenesulfonyl) Hydrogenation of the alkene moiety and subsequent methanolysis and acidic treatment provided lactone 593 Reduction of lactone 593 with (i-Bu)2NH and glycosidation with methanol furnished methyl 4-epi-N-tosyl-a-D-tolyposaminide (ỵ)-594 (Scheme 146).313 Lindstroăm and co-workers313 have presented an efficient asymmetric synthesis of the iminoalditol 599 (Scheme 147) The method requires only four steps in water, without the use of protecting groups (E,E)-1,6-Dibromohexa-2,4-diene 595 undergoes Sharpless asymmetric dihydroxylation with formation of diol 596 (70% yield, 97% ee) Upon heating in water at 50  C, the allyl bromide is hydrolyzed chemoselectively giving triol 597 Epoxidation of 597 with H2O2 in the presence of dinuclear peroxotungstate catalyst K2[W2O3(O2)4(H2O)2]314 gave 598 in 99% yield and 92% de Ammonolysis of bromide 598 in aqueous ammonia was spontaneously followed by an intramolecular ring opening of the epoxide (60% overall yield based on 595) Synthesis of Monosaccharides and Analogs AD-mix-a, NaHCO3 Br Br 595 H2O2 (1.2 equiv.) H2O, 20 ЊC K2[W2O3(O2)4(H2O)2] (0.02 equiv.) 99%, d.r 96:4 Br MeSO2NH2 H2O/t-BuOH1:1 ЊC,16 h 70%, 97% ee Br OH OH Br Br H2O 50 ЊC, h 98% OH OH OH OH 596 597 HO OH O OH 10% NH3/H2O 4h 88% 598 573 OH OH N H H 599 OH Scheme 147 Efficient asymmetric synthesis of an azasugar in water 1.13.12 Conclusion For many years, carbohydrates were very difficult synthetic targets because of their complexity arising from their stereochemistry and their multifunctionality In parallel with the recent revolution in organic synthesis, a large number of complicated and rare monosaccharides have been prepared by total, asymmetric synthesis Methods are available that allow one to reach both enantiomers of any natural or non-natural monosaccharides, including deoxyaminosugars, thiosugars, and azasugars, and this, quite offen, in a few synthetic steps Depending on the target, pure chemical procedures relying on asymmetric catalysis using either metallic or pure organic catalysts can be applied successfully, alone or in combination with chemoenzymatic methods References Butlerow, M A C R Hebd Se´ances Acad Sci 1861, 53, 145–147 Butlerow, M A Ann Chem 1861, 120, 295–298 Jones, J K N.; 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Yamaguchi, K.; Hikichi, S.; Mizuno, N Adv Synth Catal 2003, 345, 1193–1196 582 Synthesis of Monosaccharides and Analogs Biographical Sketch Inmaculada Robina received her graduate education at the University of Seville, Spain, where she also obtained her Ph.D (Organic Chemistry) in 1982 (Prof J Fdez-Bolan˜os Va´zquez, Prof J Fuentes) In 1986, she was promoted to associate professor of organic chemistry She carried out postdoctoral research in Edinburgh, UK (Prof J.G Buchanan), where she worked on the synthesis of imino sugars In 1999, she spent three months in Cambridge, UK (Prof S.V Ley), where she worked on the synthesis of oligosaccharides, in particular the synthesis of glycosyl-phosphatidoinositol anchor analogs She has been an invited professor at the University of Lausanne and at the Ecole Polytechnique Fe´de´rale de Lausanne (EPFL), Switzerland, where she worked in Prof P Vogel’s research group Her research focuses on the synthesis of oligosaccharides, especially those related to the molecular signals of the symbiosis Rhizobium-legume plant, and on the design and synthesis of enzyme inhibitors, imino-C-glycosides, imino-C-disaccharides, thiosugars, and nucleoside analogs She is also interested in the synthesis of novel oligo- and peptidomimetics Recently, she has been also involved in the synthesis of novel glycopeptides and peptidomimetics that would interfere with HIV entry Pierre Vogel spent two years at Yale University with Prof Martin Saunders after his Ph.D studies at the University of Lausanne, Switzerland (1969, Prof Horst Prinzbach) He then joined the research laboratory of Syntex in Mexico City and worked with Prof Pierre Crabbe´ He returned to the University of Lausanne where he was promoted to full professor in 1977 He has been associate professor at the Ecole Normale Supe´rieure in Paris, at the University of Paris VI, and at the University of Montpellier, France He also taught at the Universities of Rouen and Caen in Normandy and at the Ecole Polytechnique in Palaiseau near Paris He obtained the Novartis lectureship for 2003 and was elected Boehringer-Ingelheim Distinguished Lecturer for 2005 Since 2001, Prof Pierre Vogel chairs the Laboratory of Glycochemistry and Asymmetric Synthesis of the Ecole Polytechnique Fe´de´rale de Lausanne (EPFL), Switzerland He has published books and has co-authored more than 400 publications in the fields of physical organic chemistry, organic and organometallic synthesis, catalysis, glycochemistry, and bio-organic chemistry ... reaction of formaldehyde with syngas in the presence of RhCl(CO)(PPh3)2 and tertiary amines (Scheme 4).17 1.13.3 Prebiotic Synthesis of Carbohydrates The formation of Earth from a diffuse cloud of. .. enantioselective de novo synthesis of both enantiomers of natural or unnatural hexoses with up to 99% ee This implied tandem two-step sugar synthesis based on direct aminoacid-catalyzed Synthesis of Monosaccharides... Desymmetrization of meso-diacetate by lipase-catalyzed hydrolysis synthesis of C3-alditol derivatives Instead of applying enantioselective hydrolysis of meso-diacetates, monoacetylation of meso-diols