Supporting Information. Takeo Kawabata,* Wataru Muramatsu, Tadashi Nishio, Takeshi Shibata and Hartmut Schedel

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1 S-1 Content: Supporting Information Takeo Kawabata,* Wataru Muramatsu, Tadashi ishio, Takeshi Shibata and artmut Schedel Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan A catalytic one-step process for the chemo- and regioselective acylation of monosaccharides kawabata@scl.kyoto-u.ac.jp General 2 List of abbreviation 2 Procedure for the preparation of catalysts 3 (2S,5S)-1-(pyridin-4-yl)pyrrolidine-2,5-dicarboxylic acid 3 L-Tryptophan n-octyl ester 4 (2S,5S)-2,5-Bis[(2S)-3-(1-indol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbonyl]- 1-(pyridin-4-yl)pyrrolidine (1) 5 (2S,5S)-2,5-Bis[(2R)-3-(1-indol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbonyl]- 1-(pyridin-4-yl)pyrrolidine (2) 6 (2S,5S)-2,5-Bis[(2S)-3-(4-hydroxyphenyl)-1-(octyloxy)-1-oxopropan-2-ylamino]- carbonyl]-1-(pyridin-4-yl)pyrrolidine (3) 7 (2S,5S)-2,5-Bis[(2R)-3-(4-hydroxyphenyl)-1-(octyloxy)-1-oxopropan-2-ylamino]- carbonyl]-1-(pyridin-4-yl)pyrrolidine (4) 8 (2S,5S)-2,5-Bis[(2S)-3-(1-methylindol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]- carbonyl]-1-(pyridin-4-yl)pyrrolidine (5) 9 (2S,5S)-2,5-Bis[(2S)-3-(2-naphthylmethyl)-1-(octyloxy)-1-oxopropan-2-ylamino]- carbonyl]-1-(pyridin-4-yl)pyrrolidine (6) 10 (S)-octyl 3-(1-indol-3-yl)-2-((S)-1-(pyridin-4-yl)pyrrolidine-2-carboxamido)- propanoate (7) 11 Preparation of octyl 2--isobutyryl-β-D-glucopyranoside (13) and octyl 4--isobutyryl -β-d-glucopyranoside (14) 12 octyl 2--isobutyryl-β-D-glucopyranoside (13) 14 octyl 4--isobutyryl-β-D-glucopyranoside (14) 14 Preparation of octyl 3--isobutyryl-β-D-glucopyranoside (18) 15 Preparation of octyl 3--isobutyryl-β-D-glucopyranoside (19) 17

2 S- General MR spectra were obtained with a JEL JM 400 spectrometer, chemical shifts being given in ppm units (tetramethylsilane or chloroform as internal standards, indicating 0 or 7.24, respectively). IR spectra were recorded with a JACS FT/IR 300 spectrometer. Specific rotation was measured with a oriba SEPA 200 automatic digital polarimeter. MS spectra were recorded with a JEL JMS DX300 mass spectrometer. TLC analysis and preparative TLC were performed on commercial glass plates bearing a 0.25 mm layer and 0.5 mm layer of Merck Kiesel gel 60 F 254, respectively. Silica gel chromatography was carried out Wakogel C 200, Fuji Silysia BW 1277, or acalai Tesque Silica gel 60 ( mesh). Dry solvents (TF, ether, hexane, dichloromethane, and toluene; <50 ppm water contents) were purchased from Kanto Chemical C., Inc. and used without further treatment. List of abbreviations DCM TF DMF TMDMSCl TMSC TMSTf MM Bt WSC dichloromethane tetrahydrofuran dimethylforamide tert-butyldimethylsilyl chloride cyanotrimethylsilane trimethylsilyl trifluoromethansufonate -methylmorpholine 1-hydroxybenzotriazole hydrate water soluble carbodiimide 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide (EDC)

3 S- Procedure for the preparation of catalysts (2S,5S)-1-(pyridin-4-yl)pyrrolidine-2,5-dicarboxylic acid C 2 1) conc.cl (cat) Me, quant 2) 4-Bromopyridine Cl CuI, Cs 2 C 3 Me Me Dioxane, 100 C 1) DIBA, BF C 2 Me 3 Et 2 TF, -78 C 2) TMS-C, TMS-Tf DCM, r.t. C C 2 Me conc. Cl 2 C 85 C, 8 h Cl C 2 A solution of L-pyroglutamic acid (5.00 g, 38.7 mmol) and a catalytic amount (50 µl) of concentrated Cl in methanol (50 ml) was stirred at room temperature for 21 h. Evaporation of the solvent gave (S)-methyl 2-pyrrolidone-5-carboxylate* (5.56 g), which was used in the next step without further purification. A mixture of (S)-methyl 2-pyrrolidone-5-carboxylate (2.00 g, 14.0 mmol), 4-bromopyridine hydrochloride (5.40 g, 28.0 mmol), cuprous iodide (1.33 g, 7.0 mmol), and cesium carbonate (11.4 g, 35.0 mmol) in dioxane (30 ml) was stirred with Ar bubbling for 15 min.** The resulting mixture was heated under reflux of diaxane under Ar for 23 h. After cooling to room temperature, the mixture was filtered and washed with dioxane. The combined filtrate was concentrated in vacuo. The residue was purified by Si 2 column chromatography (ethyl acetate:methanol=10:1) to give (S)-methyl 5-oxo-1-(pyridin-4-yl)pyrrolidine-2-carboxylate (2.10 g, 68%). * This compound is commercially available from Aldrich. ** Klapars, A., uang, X. & Buchwald, S. L. J. Am. Chem. Soc. 124, (2002). (S)-methyl 5-oxo-1-(pyridin-4-yl)pyrrolidine-2-carboxylate: [α] D 21 = -48 (c 1.0, CCl 3 ); 1 MR (CDCl 3 ) δ 8.47 (dd, 4.9, 1.6, 2), 7.45 (dd, 4.9, 1.6, 2), 4.72 (dd, 9.0, 2.4, ), 3.73 (s, 3), (m, 3), (m, ). 13 C MR (CDCl 3 ) δ 174.8, , , , , 60.02, 53.12, 31.26, IR (neat) 3000, 1722, 1712, 1590, 1500, 1380 cm -1. EI-MS m/z (rel intensity) 220 (M +, 25), 161 (100), 133 (15), 105 (10), 78 (10); Anal Calcd for C : C, 59.99;, 5.49;, %. Found: C, 59.70;, 5.58;, % To a solution of (S)-methyl 5-oxo-1-(pyridin-4-yl)pyrrolidine-2-carboxylate (3.10 g, 14.1 mmol) in TF (50 ml) cooled at -78 C were added BF 3 Et 2 (1.90 ml, 15.0 mmol) followed by DIBA (0.94 mol/l hexane solution, 30 ml, 28.2 mmol). After

4 S- stirring for 90 min, the reaction mixture was poured into sodium potassium tartrate solution (39 g in 120 ml of 2 ) and the resulting mixture was stirred at room temperature for 1 h. The mixture was extracted with EtAc. The organic layer was washed with saturated aqueous ac 3 solution, dried over a 2 S 4, filtered and evaporated to give a crude material. To a solution of this material in C 2 Cl 2 (80 ml), were added TMSC (4.70 ml, 35.3 mmol) and TMSTf (6.40 ml, 35.3 mmol) at 0 C under Ar. After removing of the cooling bath, the mixture was stirred at room temperature for 12 h. The reaction mixture was poured into saturated aqueous ac 3 solution and stirred for additional 30 min (Caution! ydrogen cyanide is evolved). The mixture was extracted with EtAc. The organic layer was washed with saturated aqueous ac 3 solution, dried over a 2 S 4, filtered and evaporated. The residue was purified by Si 2 column chromatography (CCl 3 :Me=100:0~100:1) to give desired (2S,5S)-methyl 5-cyano-1-(pyridin-4-yl)- pyrrolidine-2-carboxylate (0.75 g, 23% overall) and its (2S,5R)-isomer (0.93 g, 29% overall). (2S,5S)-methyl 5-cyano-1-(pyridin-4-yl)- pyrrolidine-2-carboxylate: [α] 21 D = -235 (c 1.0, CCl 3 ). 1 MR (CDCl 3 ) δ 8.37 (dd, 4.8, 1.7, 2), 6.50 (dd, 4.8, 1.7, 2), 4.68 (m, ), 4.45 (m, ), 3.76 (s, 3), (m, 4). 13 C MR (CDCl 3 ) δ , , , , , 59.93, 52.91, 48.77, 29.65, IR (naet) 1740, 1595, 1510, 1380 cm -1. EI-MS m/z (rel intensity) 231 (M +, 35), 172 (100), 145 (61), 105 (10); RMS calculated for C ; , found (2S,5R)-methyl 5-cyano-1-(pyridin-4-yl)-pyrrolidine-2-carboxylate: [α] 21 D = +79 (c 1.0, CCl 3 ). 1 MR (CDCl 3 ) δ 8.30 (dd, 4.9, 1.6, 2), 6.47 (dd, 4.9, 1.8, 2), 4.55 (m, ), 4.37 (m, ), 3.73 (s, 3), (m, 4). 13 C MR (CDCl 3 ) δ , , , , , 60.43, 52.66, 48.54, 30.00, IR (neat) 1740, 1600, 1510, 1380 cm -1. EI-MS m/z (rel intensity) 231 (M +, 20), 172 (100), 145 (25); RMS calculated for C ; , found A solution of (2S,5S)-methyl 5-cyano-1-(pyridin-4-yl)- pyrrolidine-2-carboxylate (0.75 g, 3.24 mmol) in concentrated Cl (3.0 ml) was heated at 85 C for 8 h. After cooling to room temperature, the formed precipitate was collected by filteration and washed with acetone to give Cl salt of (2S,5S)-1-(pyridin-4-yl)pyrrolidine- 2,5-dicarboxylic acid (0.88 g, quant) as colorless needles. mp C. 1 MR (D 2 ) δ 8.03 (d, 6.5, 2), 6.74 (d, 6.5, 2), 4.65 (m, partially overlapping with water signal), (m, 4). 13 C MR (D 2 ) δ , , , , 62.01, 28.48; IR (KBr) 1740, 1640, 1595, 1540 cm -1. FAB-MS m/z 237 (M + ); Anal Calcd for C : C, 48.45;, 4.81;, Found: C, 48.28;, 4.92;, L-Tryptophan n-octyl ester C 2 Boc 1) n-ctanol DMAP WSC Cl 2) 2 M Cl in EtAc C 2 (C 2 ) 7 C 3 2 / Cl

5 S- To a solution of -Boc- L-trptophan (5.00 g, 16 mmol) and n-octanol (7.80 ml, 49 mmol) in DCM (50 ml) were added WSC Cl (9.50 g, 49 mmol) and DMAP (1.00 g, 8.2 mmol) at 0 C. After stirring at room temperature for 2 h, the reaction mixture was was diluted with Ethyl acetate and washed successively with 1 M aq. Cl, saturated aq. ac 3, and brine. The organic layer was dried over anhydrous a 2 S 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 4/1) to give -Boc-L-tryptophan n-octyl ester. 4 M Cl in EtAc was added to a solution of the ester at 0 C and the resulting solution was stirred at room temperature for 2 h. The solvent was evaporated in vacuo. The resulting white solid was recrystallized from EtAc to afford L-Tryptophan n-octyl ester (75%) as colorless crystals. Colorless crystals. m.p C. [α] D 20 = 15 (c 1.0, C 3 ). 1 MR (400 Mz, CD 3 D) δ 7.53 (dd, J = 8.0, 1.0 z, 1), 7.39 (dd, J = 8.0, 1.0 z, 1), 7.20 (s, 1), 7.14 (ddd, J = 8.0, 7.0, 1.0 z, 1), 7.06 (ddd, J = 8.0, 7.0, 1.0 z, 1), 4.87 (br s, 3), 4.30 (dd, J = 7.0, 6.3 z, 1), 4.15 (dt, J = 10.8, 6.8 z, 1), 4.10 (dt, J = 10.8, 6.8 z, 1), 3.43 (dd, J = 14.9, 6.3 z, 1), 3.36 (dd, J = 14.9, 7.0 z, 1), 1.52 (quintet, J = 6.8 z, 2), (m, 10), 0.90 (t, J = 7.0 z, 3). 13 C MR (100 Mz, CD 3 D) δ , , , , , , , , , 67.69, 54.76, 32.98, 30.29, 30.28, 29.40, 27.84, 26.80, 23.72, IR (KBr) 3280, 2901, 1732, 1579, 1435 cm -1. MS m/z (rel intensity) 317 (M +, 100), 317 (50), 289 (10), 188 (10), 130 (60). RMS calcd for C (M): , Found, Anal Calcd for C Cl 2 2 (Cl salt): C, 64.67;, 8.28;, Found: C, 64.45;, 8.23;, (2S,5S)-2,5-Bis[(2S)-3-(1-indol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbonyl]- 1-(pyridin-4-yl)pyrrolidine (1) 2 C Cl C 2 + C 2 (C 2 ) 7 C 3 2 Cl MM, BT WSC Cl DCM, DMF n-ct 2 C 1 C 2 n-ct To a solution of (2S,5S)-1-(pyridin-4-yl)pyrrolidine-2,5-dicarboxylic acid hydrochloride (100 mg, 0.37 mmol) in DMF-DCM were successively added was added L-tryptophan n-octyl ester hydrochloride (390 mg, 1.10 mmol), MM (240 µg, 2.20 mmol), Bt (150 mg, 1.1 mmol), and WSC Cl (210 mg, 1.1 mmol) at room temperature. The reaction mixture was stirred at room temperature for 34 h. The reaction mixture was diluted with ethyl acetate, washed saturated aqueous ac 3 and brine, dried over a 2 S 4, filtered and evaporated in vacuo. The residue was purified by Si 2 column chromatography (CCl 3 : Me = 50 : 1) to give a crude residue, which was recrystallized from EtAc to give 1 (165 mg, 54%) as colorless crystals. m.p C. [α] 20 D = 60 (c 1.0, C 3 ). 1 MR (400 Mz, CD 3 D) δ 7.45 (d, J = 8.0 z, 2), 7.39 (br s, 2), 7.24 (d, J = 8.0

6 S- z, 2), 7.00 (s, 2), 6.98 (d, J = 8.0 z, 2), 6.90 (t, J = 7.4 z, 2), 5.57 (br d, J = 5.1 z, 2), 4.65 (dd, J = 10.0, 4.8 z, 2), 4.13 (d, J = 8.0 z, 2), 4.02 (dd, J = 10.8, 6.5 z, 2), 3.96 (dd, J = 10.8, 6.5 z, 2), 3.27 (dd, J = 14.8, 4.8 z, 2), 3.04 (dd, J = 14.8, 10.0 z, 2), (m, 2), (m, 2), 1.46 (br t, J = 6.3 z, 4), (m, 20), 0.79 (t, J = 6.8 z, 6). 13 C MR (100 Mz, CD 3 D) δ , , , , , , , , , , , , , 66.52, 63.21, 54.74, 32.98, 30.35, 30.32, 29.67, 28.25, 26.97, 23.71, IR (KBr) 3308, 2855, 1735, 1657, 1601 cm -1. MS m/z (rel intensity) 833 (M +, 100), 675 (10), 489 (40), 145 (70). RMS calcd for C (M): , found, (2S,5S)-2,5-Bis[(2R)-3-(1-indol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbonyl]- 1-(pyridin-4-yl)pyrrolidine (2) n-ct 2 C C 2 n-ct m.p C. [α] D 20 = 55 (c 1.0, C 3 ). 1 MR (400 Mz, CDCl 3 ) δ 8.51 (br s, 2), 8.01 (d, J = 6.2 z, 2), 7.35 (d, 7.8 z, 2), 7.26 (d, J = 7.8 z, 2), 7.15 (t, J = 7.8

7 S- z, 2), 7.04 (t, J = 7.8 z, 2), 6.42 (br d, J = 2.2 z, 2), 6.14 (d, J = 7.5 z, 2), 6.06 (d, J = 6.2 z, 2), 4.73 (dd, J = 13.2, 6.2 z, 2), 4.07 (t, J = 6.8 z, 4), 4.01 (d, J = 7.8 z, 2), 3.19 (dd, J = 14.8, 5.3 z, 2), 3.14 (dd, J = 14.8, 6.2 z, 2), (m, 2), (m, 2), (m, 4), (m, 20), 0.88 (t, J = 6.8 z, 6). 13 C MR (100 Mz, CDCl 3 ) δ (2), (2), (2), , (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (4), (2), (2), (2), (2), (2). IR (KBr) 3309, 2855, 1737, 1663, 1600 cm -1. MS m/z (rel intensity) 833 (M +, 100), 675 (10), 489 (60), 333 (10). RMS calcd for C (M): , found, (2S,5S)-2,5-Bis[(2S)-3-(4-hydroxyphenyl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbon yl]-1-(pyridin-4-yl)pyrrolidine (3) n-ct 2 C C 2 n-ct

8 S- Colorless crystals. m.p C. [α] D 20 = 60 (c 0.5, C 3 ). 1 MR (400 Mz, CD 3 D) δ 7.83 (d, J = 5.5 z, 2), 7.07 (d, 8.7 z, 4), 6.72 (d, J = 8.7 z, 4), 5.75 (d, J = 5.5 z, 2), 4.63 (dd, J = 11.2, 4.6 z, 2), 4.30 (d, J = 7.8 z, 2), (m, 4), 3.19 (dd, J = 14.2, 4.6 z, 2), 2.79 (dd, J = 14.2, 11.2 z, 2), (m, 2), (m, 2), (m, 4), (m, 20), 0.90 (t, J = 6.9 z, 6). 13 C MR (100 Mz, CD 3 D) δ (2), (2), (2), , (2), (4), (2), (4), (2), (2), (2), (2), (2), (2), (2), (4), (2), (2), (2), (2). IR (KBr) 3299, 2855, 1737, 1660, 1604 cm -1. MS m/z (rel intensity) 787 (M +, 100), 759 (20), 466 (20), 277 (30), 241 (40). RMS calcd for C (M): , found, (2S,5S)-2,5-Bis[(2R)-3-(4-hydroxyphenyl)-1-(octyloxy)-1-oxopropan-2-ylamino]- carbonyl]-1-(pyridin-4-yl)pyrrolidine (4) n-ct 2 C C 2 n-ct Colorless crystals, m.p C. [α] D 20 = 58 (c 0.4, C 3 ). 1 MR (400 Mz, CD 3 D) δ 8.00 (d, J = 5.5 z, 2), 6.91 (d, 8.2 z, 4), 6.64 (d, J = 8.2 z, 4), 6.32 (d,

9 S- J = 5.5 z, 2), 4.61 (dd, J = 10.1, 5.0 z, 2), 4.37 (d, J = 7.8 z, 2), (m, 4), 3.09 (dd, J = 13.7, 5.0 z, 2), 2.82 (dd, J = 13.7, 10.1 z, 2), (m, 2), (m, 6), (m, 20), 0.89 (dd, J = 6.9, 6.0 z, 6). 13 C MR (100 Mz, CD 3 D) δ (2), (2), (2), , (2), (4), (2), (4), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2). IR (KBr) 3309, 2855, 1739, 1660, 1603 cm -1. MS m/z (rel intensity) 787 (M +, 100), 759 (40), 466 (20), 277 (20), 241 (30). RMS calcd for C (M): , found, (2S,5S)-2,5-Bis[(2S)-3-(1-methylindol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbo nyl]-1-(pyridin-4-yl)pyrrolidine (5) Me Me Colorless crystals. m.p C. [α] D 21 = 17 (c 0.6, CCl 3 ). 1 MR (400 Mz, CDCl 3 ) δ 8.00 (d, J = 6.3 z, 2), 7.43 (d, 7.8 z, 2), 7.24 (d, J = 7.8 z, 2), 7.19 (ddd, J = 7.8, 6.8, 1.0 z, 2), 7.11 (ddd, J = 7.8, 6.8, 1.0 z, 2), 6.66 (s, 2), 5.88 (d, J = 6.3

10 S- z, 2), 5.85 (d, J = 8.0 z, 2), 4.70 (dt, J = 8.0, 5.8 z, 4), 4.09 (t, J = 6.9 z, 4), 3.65 (s, 6), (m, 2), 3.27 (dd, J = 15.0, 5.8 z, 2), 3.17 (dd, J = 15.0, 5.8 z, 2), (m, 4), (m, 4), (m, 20), 0.88 (t, J = 6.9 z, 6). 13 C MR (100 Mz, CDCl 3 ) δ (2), (2), (2), , (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (4), (2), (2), (2), (2), (2), (2). IR (KBr) 3312, 2926, 1743, 1657, 1599 cm -1. MS m/z (rel intensity) 861 (M + +, 100), 503 (50), 314 (10), 144 (100). RMS Calcd for C : , Found, (2S,5S)-2,5-Bis[(2S)-3-(2-naphthylmethyl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbo nyl]-1-(pyridin-4-yl)pyrrolidine (6) Colorless Crystals. m.p C. [α] D 20 = 51 (c 0.9, C 3 ). 1 MR (400 Mz, CDCl 3 ) δ 7.88 (d, J = 6.3 z, 2), (m, 2), 7.74 (br d, J = 8.7 z, 2), (m, 2), (m, 6), 7.15 (dd, J = 8.4, 1.6 z, 2), (m, 2), 6.01 (J = 6.3 z, 2), 4.81 (dd, J = 13.3, 7.0 z, 2), (m, 6), 3.35 (dd, J = 14.0,

11 S- 5.8 z, 2), 3.14 (dd, J = 14.0, 7.0 z, 2), (m, 4), (m, 4), (m, 20), 0.88 (t, J = 6.9 z, 6). 13 C MR (100 Mz, CDCl 3 ) δ (2), (2), (2), 149.5, (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), (2), 66.0 (2), 62.2 (2), 52.7 (2), 37.7 (2), 31.8 (2), 29.1 (4), 28.9 (2), 28.4 (2), 25.8 (2), 22.6 (2), 14.1 (2). IR (KBr) 3307, 2925, 1734, 1655, 1599 cm -1. MS m/z (rel intensity) 855 (M + +, 100), 827 (10), 500 (30), 145 (100), 120 (80). RMS Calcd for C : , Found, Anal Calcd for C : C, 74.44;, 7.78;, Found: C, 74.18;, 7.92;, (S)-ctyl 3-(1-indol-3-yl)-2-((S)-1-(pyridin-4-yl)pyrrolidine-2-carboxamido)- propanoate (7) Colorless crystals. m.p C. [α] 20 D = -70 (c 1.0, C 3 ). 1 MR (400 Mz, CD 3 D) δ 7.88 (d, J = 6.3 z, 1), 7.53 (d, J = 8.0 z, 1), 7.35 (d, J = 8.0 z, 1), 7.12 (ddd, J = 8.0, 7.0, 1.0, 1), 7.07 (s, 1), 7.02 (ddd, J = 8.0, 7.0, 1.0 z, 1), 6.20 (d, J = 6.3 z, 1), 4.75 (dd, J = 9.3, 5.2 z, 1), (t, J = 6.5 z, 1), (t, J = 6.5 z, 1), (m, J = 1), (m, 1), 3.37 (dd, J = 14.7, 5.2 z, 1),

12 S- (m, 1), 3.19 (dd, J = 14.7, 9.3 z, 1), (m, 1), (m, 1), (m, 1), (m, 1), (m, 2), (m, 10), 0.90 (t, J = 6.9 z, 3). 13 C MR (100 Mz, CD 3 D) δ , , , (2), , , , , , , , , (2), 66.58, 63.10, 54.74, 48.61, 32.01, 32.27, (2), 29.70, 28.03, 27.00, 24.48, 23.76, IR (KBr) 3279, 2925, 2855, 1741, 1667, 1600 cm -1. MS m/z (rel intensity) 490 (M +, 10), 361 (30), 147 (100), 130 (30). RMS Calcd for C : , Found, Preparation of octyl 2--isobutyryl-β-D-glucopyranoside (13) and octyl 4--isobutyryl-β-D-glucopyranoside (14) C 8 17 TBDMSCl (1.1 eq) Imidazole (2 eq) DMF 0 C, 0.5 h (100%) TBS C Methoxypropene (1.3 eq) PPTS (5 mol%) DMF rt, 2 h (78%, 9 : 10 = 5 : 9) TBS C TBS 10 C 8 17 Isobutyryl chloride (3 eq) 2,4,6-Collidine (3 eq) DMAP (5 mol%) C 2 Cl 2 rt, 16 h (99%) TBS TBS C C 8 17 CSA- 2 (5 mol%) 0 C, 2 h C C (34%) 14 (59%)

13 S- Imidazole (140 mg, 2.1 mmol) and TBDMSCl (170 mg, 1.13 mmol) were added to a solution of octyl β-d-glucopyranoside (70 mg, 0.24 mmol) in DMF (7mL) cooled at 0 C under 2. After stirring for 30 min, the reaction mixture was quenched with saturated aqueous 4 Cl and extracted with ethyl acetate. The organic layer was dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 1/1 ~0/1) to give 8 (416 mg, 100%). Colorless crystals. m.p C. [α] D 21 = -37 (c 1.0, CCl 3 ). 1 MR (300 Mz, CDCl 3 ) δ 4.26 (d, J = 7.7 z, 1), 3.87 (d, J = 8.3 z, 2), (br s, 1), (m, 1), (m, 3), (m, 2), (m, 2), (m, 10), 0.90 (s, 9), 0.88 (t, J = 7.0 z, 3), (s. 3), (s, 3). 13 C MR (75 Mz, CDCl 3 ) δ , 76.29, 74.58, 73.46, 72.40, 70.04, 64.42, 31.80, 29.59, 29.36, 29.22, 25.93, 25.82, (3), 18.22, 14.07, (2). IR (KBr) 3396, 2927, 2856, 1637, 1463 cm -1. MS m/z (rel intensity) 407 (M +, 20), 277 (80), 259 (100). RMS calcd for C Si (M): , found, Anal Calcd for C Si: C, 59.07;, Found: C, 59.26;, To a solution of 8 (340 mg, 0,84 mmol) in DMF (8 ml) were added 2-methoxypropene (104 µl) and PPTS (10.5 mg, 0,041 mmol) under 2. After stirring at room temperature for 2 h, the reaction mixture was quenched with saturated aqueous ac 3 and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 95/5 ~70/30) to give a mixture of 9 and 10 (291 mg, 78%, 9:10=5:9). To a solution of the mixture of 9 and 10 (220mg, 0,49 mmol) in DCM (5.0 ml) were successively added 2,4,6-cllidine (196 µl, 1.48 mmol), DMAP (3.0 mg, mmol), and isobutyryl chloride (155 µl, 1.48 mmol) at 0 C under 2. After stirring at room temperature for 16 h, the reaction mixture was quenched with saturated aqueous 4 Cl and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 90/10) to give a mixture of 11 and 12 (251 mg, 99%, 11:12=5:9). The mixture of 11 and 12 (251 mg, 11:12=5:9) was dissolved in Me (10 ml). CSA 2 (5.6 mg, mmol) was added to the solution at 0 C, and the resulting mixture was stirred at 0 C for 2 h. After evaporation of the solvent, the residue was purified by Si 2 column chromatography (n-hexane/etac = 50/50~0/100) to give pure 13 (60 mg, 34%) and pure 14 (104 mg, 59%), respectively.

14 S- ctyl 2--isobutyryl-β-D-glucopyranoside (13): Colorless crystals. m.p C. [α] D 22 = 41 (c 1.0, CCl 3 ). 1 MR (400 Mz, CDCl 3 ) δ 4.74 (dd, J = 9.3, 8.0 z, 1), 4.43 (d, J = 8.0 z, 1), 4.34 (br s, 1), 3.99 (br s, 1/2), (m, 2), 3.50 (dt, J = 9.7, 6.5 z, 1), 3.67 (br t, J = 9.2 z, 1), 3.59 (br t, J = 9.4 z, 1), 3.43 (dt, J = 9.7, 6.9 z, 1), 3.33 (dt, J = 9.2, 3.4 z, 1), 3.19 (br s, 1/2), 2.60 (hept, J = 7.0 z, 1), 2.25 (br s, 1), (m, 2), (m, 10), 1.19 (s, 3), 1.18 (s, 3), 0.88 (t, J = 6.8 z). 13 C MR (100 Mz, CDCl 3 ) δ , , 77.23, 75.38, 73.73, 70.49, 70.18, 61.76, 34.09, 31.83, 29.56, 29.38, 29.24, 25.93, 22.65, 19.04, 18.81, IR (KBr) 3510, 2930, 1725, 1469, 1212 cm -1. MS m/z (rel intensity) 363 (M +, 10), 233 (100), 215 (10). RMS calcd for C (M): , found, Anal Calcd for C : C, 59.65;, Found: C, 59.60;, ctyl 4--isobutyryl-β-D-glucopyranoside (14): Colorless crystals. m.p C. [α] D 21 = 28 (c 1.0, CCl 3 ). 1 MR (400 Mz, CDCl 3 ) δ 4.85 (t, J = 9.7 z, 1), 4.32 (d, J = 7.8 z, 1), 3.89 (dt, J = 9.4, 7.0 z, 1), 3.69 (t, J = 8.8 z, 2), 3.53 (dt, J = 9.4, 7.0 z, 1), (m, 3), 2.65 (br s, 1), 2.62 (hept, J = 7.0, 1), 1.63 (quint, 7.0 z, 2), (m, 10), (d, J = 7.0 z, 3), (d, J = 7.0 z, 3), 0.88 (t, J = 6.9 z, 3). 13 C MR (100 Mz, CDCl 3 ) δ , , 74.41, 74.23, 74.16, 70.60, 70.42, 61.46, 34.05, 31.83, 29.60, 29.41, 29.26, 25.93, 22.66, 19.00, 18.85, IR (KBr) 3501, 2925, 2857, 1742, 1469 cm -1. MS m/z (rel intensity) 363 (M +, 10), 233 (100), 215 (5). RMS calcd for C (M): , found,

15 S- Preparation of octyl 3--isobutyryl-β-D-glucopyranoside (18) C 8 17 p-me-ph 16 C 8 17 p-me-phc(me) 2 (1.1 eq) PPTS (5 mol%) C DMF rt, 2 h (99%) p-me-ph + p-me-ph 17 C C 8 17 C 8 17 Isobutyryl chloride (1.5 eq) 2,4,6-Collidine (1.5 eq) DMAP (5 mol%) C 2 Cl 2 0 C, 3 h (61%, 16 : 17 = 2 : 7) CSA- 2 (5 mol%) Me 0 C, 2 h 18 (20%) 13 (73%) A solution of octyl β-d-glucopyranoside (250 mg, 0.86 mmol), p-anisaldehyde dimethyl acetal (0.16 ml, 0.94 mmol) and PPTS (11 mg, mmol) in DMF (10 ml) was stirred at room tyemperature for 2 h. The reaction mixture was quenched with saturated aqueous ac 3 and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 50/50) to give 15 (348 mg, 99%). To a solutiuon of 15 (356 mg, 0.87 mmol) in DCM (9.0 ml) were successively added 2,4,6-colloidine (0.17 ml, 1.30 mmol), DMAP (5.3 mg, mmol) and isobutyryl chloride (136 µl, 1.30 mmol) at 0 C. After stirring at 0 C

16 S- for 3 h, the reaction mixture was quenched with saturated aqueous 4 Cl and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (n-hexane/etac = 90/10~70/30) to give a mixture of 16 and 17 (253 mg, 61%, 16:17=2:7). The mixture of 16 and 17 (186 mg, 0.39 mmol) was dissolved in Me (8 ml). CSA 2 (4.5 mg, mmol) was added to the solution at 0 C, and the resulting mixture was stirred at 0 C for 2 h. After evaporation of the solvent, the residue was purified by Si 2 column chromatography (n-hexane/etac = 50/50~0/100) to give 13 (28 mg, 20%) and 18 (102 mg, 73%), respectively. ctyl 3--isobutyryl-β-D-glucopyranoside (18): Colorless oil. [α] 21 D = 1.8 (c 1.0, CCl 3 ). 1 MR (400 Mz, CDCl 3 ) δ 4.90 (t, J = 9.3 z, 1), 4.37 (d, J = 7.8 z, 1), (m, 2), 3.90 (dt, J = 9.4, 6.8 z, 1), 3.67 (br t, J = 9.3 z, 1), 3.56 (dt, J = 9.4, 6.8 z, 1), 3.49 (br t, J = 8.7 z, 1) 3.42 (ddd, J = 9.7, 4.6, 3.6 z) 3.12 (br s, 1), 2.67 (hept, J = 7.0 z, 1), 2.52 (br s, 1), 1.81 (br s, 1), (m, 2), (m, 10), 1.22 (d, J = 0.7 z, 3), 1.21 (d, J = 0.7 z, 3), 0.88 (t, J = 6.9 z, 3). 13 C MR (100 Mz, CDCl 3 ) δ , , 78.03, 75.72, 72.20, 70.53, 69.79, 62.34, 34.15, 31.80, 29.61, 29.36, 29.22, 25.93, 22.64, 18.95, 18.92, IR (neat) 3438, 2928, 2857, 1731, 1469 cm -1. MS m/z (rel intensity) 363 (M +, 20), 233 (100), 215 (10), 185 (20), 145 (80). RMS calcd for C (M): , found,

17 S- Preparation of octyl 6--isobutyryl-β-D-glucopyranoside (19) C 8 17 Isobutyryl chloride (1 eq) 2,4,6-Collidine (1 eq) DMAP (5 mol%) C 2 Cl 2 0 C, 4.5 h (42%) To a solutiuon of octyl β-d-glucopyranoside (70 mg, 0.24 mmol) in DCM (9.0 ml) were successively added 2,4,6-colloidine (32 µl, 0.24 mmol), DMAP (1.5 mg, mmol), and isobutyryl chloride (25 µl, 0.24 mmol) at 0 C. After stirring at 0 C for 4.5 h, the reaction mixture was quenched with saturated aqueous 4 Cl and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgS 4, filtered, and concentrated in vacuo. The residue was purified by Si 2 column chromatography (EtAc) to give 19 (36 mg, 42%). Colorless crystals. m.p C. [α] D 21 = -49 (c 1.0, CCl 3 ). 1 MR (400 Mz, CDCl 3 ) δ 4.61 (br s, 1), 4.37 (dd, J = 12.1, 2.5 z, 1), 4.32 (dd, J = 12.1, 5.8 z, 1), 4.26 (d, J = 7.8 z, 1), 4.19 (m, 1), 3.84 (dt, J = 9.4, 7.0 z, 1), 3.76 (br s, 1), (m, 1), 3.51 (dt, J = 9.4, 7.3 z, 1), 3.46 (dd, J = 5.8, 2.7 z, 1), 3.36 (t, J = 8.7 z, 2), 2.60 (hept, J = 7.0, 1), (m, 2), (m, 10), 1.18 (d, J = 7.0 z, 3), 1.17 (d, J = 7.0 z, 3), 0.88 (t, J = 6.8 z, 3). 13 C MR (100 Mz, CDCl 3 ) δ , , 76.16, 73.89, 73.53, 70.37, 70.31, 63.52, 33.95, 31.84, 29.62, 29.41, 29.28, 25.92, 22.65, 19.03, 18.95, IR (KBr) 3496, 2925, 2854, 1735, 1469 cm -1. MS m/z (rel intensity) 363 (M +, 10), 233 (100), 215 (20). RMS calcd for C (M): , found, C