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. Hz, 3.23 (qq, 1H, 3 JH2'-H3'a = 6.9 Hz, 3 JH2'-H3'b = 7.1 Hz, H2'), 3.35 (brs, 1H, OH), 3.50-3.60 (m, 4H, H-1, H3, H4 and H5), 3.68 (dd, 1H, 2 JH6a-H6b = 10.9 Hz, 2 JH4-H3 = 3.7 Hz, H6a), 3.75 (dd, 1H, 2 JH6b-H6a = 10.9 Hz, 3 JH6b-H5 = 1.7 Hz, H6b)

. Hz,

C. Nmr, C-2), 73.6 (CH2Ph), 86.0 (C-5), 127.7 (CHAr), 127.8 (2C, CHAr), vol.18

. Hrms-(esi,

3. 2s and . 4s, 6R)-4,5-bis(benzyloxy)-6-(benzyloxymethyl)-3-hydroxytetrahydro-2H-pyran-2-yl)-(phenyl)methanone 57 (62.6 mg, 0.12 mmol, 39 %) as a white solid

, Procedure B, the reaction between glucosyl cyanide 44 (285 mg, 0.62 mmol) and a solution of phenyllithium in dibutyl ether (1.2 M, 1.6 mL, 1.86 mmol), p.methanone

H. Nmr, CDCl3): ? 2.80 (s, 1H, OH), 3.59 (ddd, 1H, 3 JH5-H4 = 9, MHz, vol.3, issue.400, pp.5-6

. Hz, , p.1

, JH6a-H6b = 10.9 Hz, 3 JH6a-H5 = 5.3 Hz, H6a), 3.80 (dd, 1H, 2 JH6b-H6a = 10.9 Hz, 3 JH6b-H5 =

, Hz, H6b), 3.93 (dd, 1H, 3 JH4-H5 = 9.8 Hz, 3 JH4-H3 = 9

. Hz,

C. Nmr, CDCl3): ? 67.8 (C-1), 69.3 (C-6), 71.6 (CH2Ph), MHz, vol.73, issue.400

, 127.6 (CHAr), 127.7 (2C, CHAr), 127.8 (CHAr), vol.75, pp.82-88

, 2C, CHAr), 129.8 (2C, CHAr), 133.3 (2C, CHAr), 135.7 (CqAr), 137.6 (CqAr), vol.128

, HRMS (ESI) calculated for C34H34NaO6

, Access to aryl-keto-C-glycosides

, Preparation of organomagnesium reagents: At 0 °C, to a solution of magnesium in dry THF was added dropwise a solution of aryl halides in THF. After adding, the resulting mixture was then refluxing during 2 hours. The resulting solution was then titrated and added to the substrate following the procedure A. Preparation of organolithium reagent: At -78 °C, to a solution of aryl halide in dry THF, under argon was added slowly a solution of n-butyllithium, The resulting solution was stirred C38H36O6

, 69 g.mol -1 Brown solid Rf = 0.40 (cyclohexane/EtOAc, 8:2) m, pp.79-80

, 217 mmol) and a freshly prepared solution of naphthalen-2-ylmagnesium bromide in THF (4.64 mL, 0.65 mmol) led to 1-((2R,3R,4S,5S,6R)-4,5-bis(benzyloxy)-6-(benzyloxymethyl)-3-hydroxytetrahydro-2H-pyran-2-yl)-(naphthalene-2-yl, Procedure A, the reaction between gluconitrile 33 (100 mg

, 44 mmol) and a freshly prepared solution of naphthalen-2-yllithium in THF (6.8 mL, 1.3 mmol) led to ((2R,3R,4S,5S,6R)-4,5-bis(benzyloxy)-6-(benzyloxymethyl)-3-hydroxytetrahydro-2H-pyran-2-yl)-(naphthalene-2-yl)methanone 55, Procedure B, the reaction between gluconitrile 33

H. Nmr,

, JH4-H5 = 9.5 Hz, H4), 3.63 (dd, 1H, 2 JH6a-H6b = 11.0 Hz, 3 JH6a-H5 = 5.9 Hz, H6a), 3.77-3.85 (m, 3H, H-3, H5 and H6b

. Hz, J = 10.9 Hz, CHHPh), 5.06 (d, 1H, 2 J = 11.2 Hz, CHHPh), 7.21-7.44 (m, 15H, HAr), 7.46-7.48 (m, 1H, HAr), 7.57-7.61 (m, 1H, HAr), vol.1, pp.3-7

. Hz,

C. Nmr, 100.6 MHz, CDCl3) ? 69.5 (C-6), 72.6 (C-2), 73.7 (CH2Ph), 75.4 (CH2Ph), 75.7 (CH2Ph), 77.7 (C-4), vol.80

C. and C. ). , 2C, CHAr), 130.2 (CHAr), 132.5 (CHAr), 132.5 (CqAr), vol.127

, HRMS (ESI) calculated for C38H37O6, pp.589-2576

, Hz, H6a), 3.64 (dd, 1H, 2 JH6a-H6b = 9.7 Hz, 3 JH5-H6b = 6.2 Hz, H6b), 3.66 (dd, vol.1, pp.2-3

. Hz, JH3-H4 = 2.6 Hz, H3), 3.81 (dd, 1H, 2 JH5-H6b = 6.2 Hz, 3 JH5-H6a = 6.1 Hz, H5), 4.04 (d, 1H, 3 JH4-H3 = 2.6 Hz,H4), 4.42 (d, 1H, 2 J = 11.7 Hz, CHHPh), vol.3

C. Nmr, MHz, CDCl3):??? 68.9 (C-2), 69.4 (C-6), 72.8 (CH2Ph), vol.100

, 74.7 (CH2Ph), 78.7 (C-5), vol.82

, 8 (CHAr), 2C, CHAr), 127.6 (2C, CHAr), 127.7 (2C, CHAr), vol.127

, 132.5 (CqAr), 135.7 (CqAr), 137.8 (CqAr), 138.3 (CqAr), vol.138, p.196

, HRMS (FD + ) Calcd for C38H36O6

H. Nmr, 400 MHz, CDCl3): 3.59 (dd, 1H, 2 JH6a-H6b = 9.5 Hz, 3 JH6a-H5 = 6.4 Hz, H6a), 3.62 (dd, 1H, 2 JH6b-H6a = 9, vol.3, pp.3-4

, Hz, H3), 3.80 (ddd, 1H, 3 JH5-H6a = 6.4 Hz, 3 JH5-H6b = 6.2 Hz, 3 JH5-H4 = 0.5 Hz, H5), 4.01 (dd, 1H, 3 JH4-H3 = 2.8 Hz, 3 JH4-H5 = 0.9 Hz, H4), 4.38 (d, 1H, 2 J = 11.7 Hz, CHHPh)

, JH9-H11 = JH9-H12 = 1.1 Hz, H9), 8.65 (ddd, 1H, 3 JH12-H11 = 4.8 Hz, 4 JH12-H10 = 1.7 Hz, p.12

. Hz,

C. Nmr, MHz, CDCl3): ??68.9 (C-6), 69.0 (C-2), 72.6 (CH2Ph), vol.73

, 4 (CHAr), 127. (2C, CHAr), 127.6 (3C, CHAr), 127.8 (2C, CHAr), 74.5 (CH2Ph), 78.3 (C-1 and C-5), vol.84, pp.123-126

, HRMS (FD + ) Calcd for C33H33NO6

, 3R,4R,5S,6R)-4,5-bis(benzyloxy)-6-(benzyloxymethyl)-3-hydroxytetrahydro-2H-pyran-2-yl, p.65

H. Nmr, 400 MHz, CDCl3): 2.96 (d, 1H, 3 JOH-H2 = 2.6 Hz, OH), 3.61 (dd, 1H, 2 JH6a-H6b = 9

. Hz, JH6a-H5 = 6.1 Hz, H6a), 3.62 (dd, 1H, 3 JH3-H2 = 9.4 Hz, 3 JH3-H4 = 2.7 Hz, H3), 3.73 (dd, vol.3, p.1

, JH6b-H6a = 9.5 Hz, 3 JH6b-H5 = 6.5 Hz, H6b), 3.84 (dd, 1H, 2 JH5-H6b = 6.5 Hz, 3 JH5-H6a = 6.1 Hz, H5)

. Hz, , pp.3-5

C. Nmr, MHz, CDCl3): ??69.4 (C-2 and C-6), vol.72, pp.73-80

, 122.7 (CHAr), 123.1 (CHAr), 123.7 (CHAr), 123.8 (2C, CHAr), 124.7 (2C, CHAr), 125.4 (2C, CHAr), 126.5 (CHAr), 127.6 (CHAr), 127.7 (CHAr), 127.8 (CHAr), vol.82

, HRMS (FD + ) Calcd for C36H34O6S

. Hz, JH1-H2 = 9.4 Hz, H1), 3.42-3.50 (m, 3H, H5 and H6), 3.58 (dd, 1H, 3 JH3-H2 = 9.5 Hz, 3 JH3-H4 = 2.9 Hz, H3), vol.3

C. Nmr, 7 (CH3), 69.1 (C-6), 100.6 MHz, CDCl3) ? 20.0 (CH3), vol.29

, CHAr), 127.3 (CHAr), 127.4 (2C, CHAr), 127.5 (3C, CHAr), vol.127, pp.100-101

, HRMS (ESI): calculated for C37H40O6

, JH2-H3 = 9.7 Hz, H2), 7.22-7.38 (m, 17H, HAr), vol.3, pp.50-759

C. Nmr, 100.6 MHz, CDCl3) ? 20.8 (CH3), 68.7 (C-6), 69.5 (C-2), vol.72

, C-1), 127.5 (2C, CHAr), 127.6 (2C, CHAr), CH2Ph), 74.7 (CH2Ph), vol.73

, HRMS (ESI): calculated for C36H35O7

, 14 mmol, 78 %)

H. Nmr, 400 MHz, CDCl3): ? 3.60 (d, 2H, 3 JH6-H5 = 6.4 Hz, H6), 3.71-3.76 (m, 2H, H2 and H5

A. Dondoni, N. Cartozzi, and A. Marra, J. Org. Chem, vol.70, pp.9257-9268, 2005.

N. Lebrasseur, G. Fan, M. Oxoby, M. A. Looney, and S. Quideau, Tetrahedron, vol.61, pp.1551-1562, 2005.

G. Lejeune, J. Font, T. Parella, R. Alibés, and M. Figueredo, J. Org. Chem, vol.80, pp.3-4, 2015.

H. Nmr,

, JH2-OH = 2.8 Hz, OH), 3.52 (dd, 1H, 2 JH6a-H6b = 9.4 Hz, 3 JH5-H6a = 6.0 Hz, H6a), 3.55 (dd, p.1

, JH6a-H6b = 9.4 Hz, 3 JH5-H6a = 6.8 Hz, H6b), 3.60 (dd, 1H, 3 JH2-H3 = 9.5 Hz, 3 JH3-H4 = 2.8 Hz, H3), 3.71-3.76 (m, 1H, H5), 3.83 (d, 1H, 2 J =15.7 Hz, CHHPh)

. Hz, 2H, HAr), 6.93-6.96 (m, 2H, HAr), 7.12 (d, 1H, 3 J = 7.9 Hz, HAr), 7.22-7.42 (m, 15H, HAr), vol.7

C. Nmr, 100.6 MHz, CDCl3): ? 14.9 (CH3), 20.0 (CH3), 38.5 (CH2), vol.63, p.205

, 74 (CHAr), 127.8 (CHAr), 128.11 (CHAr), 128.15 (CHAr), CHAr), 129.5 (CHAr), 130.3 (CHAr), 131.2 (CHAr), 131.5 (CqAr), 133.1 (CqAr), vol.127, p.61

, HRMS, vol.94, p.95

, In a degazed Schlenk of 10 mL was added p-allylanisole (60 µL, 0.300 mmol) and degazed

, The resulting solution was degazed before a solution of compound 17 (128 mg, 0.216 mmol) in degazed CH2Cl2 (1.5 mL) and Grubb's II catalyst (20 mg, 0.024 mmol ) was added. The reaction mixture was heated at 39°C for 18h before diluting with dichloromethane. Silica (0.5 g) was added, and the solvent was removed. The residue was purified by column chromatography (cyclohexane/Ethyl Acetate, 95:5?90/10) to furnish compound 94 (52.5 mg, 0.075 mmol, 35%) as a brown oil

, mmol, 16%) and a mixture of both compounds (18.2 mg)

, 3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)

, 84 g.mol -1 Brown oil Rf = 0, vol.46

H. Nmr, 400 MHz, CDCl3): ??3.39-3.43 (m, 1H, H4'a), 3.43-3.47 (m, 1H, H4'b), 3.51 (ddd, 1H, 3 JH5-H4 = 9.8 Hz, 3 JH5-H6a = 4.5 Hz, 3 JH5-H6b = 2.8 Hz, H5), 3.58-3.64 (m, 1H, H4), 3.67 (dd, 1H, 2 JH6a-H6b = 11.1 Hz, 3 JH6a-H5

. Hz,

. Hz, JH3'-H4' = 6.7 Hz, H3'), 7.14-7.40 (m, 20H, HAr), vol.2

C. Nmr, 3 (CH2Ph), 75.8 (CH2Ph), 78.1 (C-4), 79.6 (C-5), 100.6 MHz, CDCl3): ??38.2 (C-4'), 55.4 (CH3), 69.1 (C-6), 73.6 (CH2Ph), 75.0(CH2Ph), vol.75

, HRMS (ESI) Calcd for C45H46NaO7

, 84 g.mol -1 Brown oil Rf = 0.35 (cyclohexane/EtOAc, vol.8

H. Nmr, 400 MHz, CDCl3): ??3.55-3.60 (m, 1H, H4'a), 3.43-3.47 (m, 1H, H4'b), 3.51 (ddd, 1H, 3 JH5-H4 = 9.8 Hz, 3 JH5-H6a = 4.5 Hz, 3 JH5-H6b = 2.8 Hz, H5), vol.1, p.2

. Hz,

?. Hrms, ESI) Calcd for C45H46NaO7

, 25 g.mol -1 Colorless oil Rf = 0.41 (cyclohexane/EtOAc, vol.8

, Under argon, to a solution of 2,3,4,6-tetra-O-benzyl-d-gluconolactone 107 (1.14 g, vol.2, p.11

, The reaction mixture was stirred for 1h at 0°C and a saturated aqueous NH4Cl solution (12 mL) was added. The resulting solution was extracted with ethyl acetate and the aqueous layer was extracted with ethyl acetate two times. The combined organic phases were washed with a saturated aqueous NaCl solution, dried over MgSO4 then concentrated. The crude product was then dissolved in dry acetonitrile (4 mL) then triethylsilane (680 µL, 4.26 mmol) and BF3.OEt2 (270 µL, 2.19 mmol) were added at 0°C under argon. The solution was stirred at room temperature for 5h before adding ethyl acetate (20 mL) and a saturated aqueous NaHCO3 solution (10 mL), dry THF (11 mL) at 0°C was added ethynylmagnesium bromide in THF solution (0.38 M, 9 mL, 3.42 mmol)

. Mgso4, The crude product was purified by column chromatography (cyclohexane/ethyl acetate, 90:10) to led to compound 108 (279.6 mg, vol.0, p.510

H. Nmr, MHz, CDCl3): ???2.54 (d, 1H, 4 JH2'H1 = 2.2 Hz, H2'), 3.45-3.49 (m, 1H, H5), 3.61-3.72 (m, 5H, H2, H3, H4, H6a, H6b)

T. Nishikawa, Y. Koide, S. Kajii, K. Wada, M. Ishikawa et al., Org. Biomol. Chem, vol.3, p.109, 2005.

, 81 g.mol -1 White solid Rf = 0.28 (cyclohexane/EtOAc, 8:2) m.p, pp.102-103

, Under argon, to a solution of 2,3,4,6-tetra-O-benzyl-1-ethynyl-?-D-glucopyranose 108 (120 mg ; 0.220 mmol) dry toluene (2 mL) was added the chlorooxime 97

, The solution was heated at 85°C overnight and then solvent was evaporated. The residue was taken up in CH2Cl2, and the organic layer was washed with HCl 1N and brine, dried over Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography, mmol) and triethylamine (40 µL, 0.273 mmol), vol.8

H. Nmr, 400 MHz, CDCl3): ???3.58-3.63 (m, 1H, H5), 3.71-3.83 (m, 5H, H6a, H6b, vol.3, p.4

. Hz,

C. Nmr, C-6), 75.2 (C-1), 100.6 MHz, CDCl3): ??55.4 (OCH3), vol.68

, 1 (CHAr), 127.8 (CHAr), CqAr), 138.1 (CqAr), 138.5 (CqAr), vol.114, pp.121-126

, 1H, 2 JH6b-H6a = 11.0 Hz, 3 JH6b-H5 = 2.5 Hz, H6b), 3.92 (dd, 1H, 3 JH3-H2 = 6.5 Hz, vol.3, pp.3-4

. Hz,

. Hz,

C. Nmr, 100.6 MHz, CDCl3), ? 68.6 (C-6), 73.6 (CH2Ph), 73.7 (CH2Ph), 73.8 (CH2Ph), 74.0 (CH2Ph), vol.76

T. C. Ho, H. Kamimura, K. Ohmori, and K. Suzuki, Org. Lett, vol.18, pp.4488-4490, 2016.