the reagents used come from the companies sigma - aldrich , acros and alfa aesar and are employed without purification . the anhydrous solvents , except for dichloromethane and thf , are purchased in the acroseal ® format from acros . dichloromethane is distilled under an inert atmosphere in the presence of calcium hydride . thf is distilled under an inert atmosphere in the presence of sodium and benzophenone . thin - layer chromatography was carried out on silica plates with merck 60 f 254 aluminum support . the techniques used to reveal the products after elution are : for the saccharide derivatives : h 2 o / 96 % h 2 so 4 /( nh 4 ) 4 ce ( so 4 ). 2h 2 o /( nh 4 ) 6 mo 7 o 24 . 4h 2 o ( 188 ml / 12 ml / 2 . 1 g / 5 . 3 g ) and then heating . for the solanidine derivatives : dragendorf &# 39 ; s reagent according to munier and macheboeuf . solution a : dissolve 0 . 85 g of bismuth nitrate in 10 ml of acetic acid and 40 ml of water . solution b : dissolve 8 g of potassium iodide in 20 ml of water . vaporization solution : solution a / solution b / acoh / h 2 o ( 1 ml : 1 ml : 4 ml : 20 ml ). conventional purifications are carried out using glass columns filled with silica gel ( gerudan geruran si 60 , 0 . 040 - 0 . 062 mm particle size , merck ). the crude reaction product is dissolved in a minimum of solvent in order to be introduced at the top of the column or to be adsorbed on silica and then introduced at the top of the column . the elution is achieved by passing an elution gradient under air pressure ( 0 . 8 bar ). automatic flash purifications were performed using the reveleris ® ies flash system ( grace ). separation is accomplished using commercially available prepacked columns of silica or c - 18 ( 4 g , 12 g , 24 g , 40 g , 80 g ). the purifications can be normal phase or reversed phase . the mass of the purifiable products corresponds to at most 10 % of the mass of the silica of the prepacked column . the purifications are carried out at a mean pressure of 50 psi ( which may be up to 200 psi ). this system is equipped with a light - scattering detector ( lsd ) and an adjustable dual - wavelength uv detector . the purifications were carried out by centrifugal partition chromatography using an armen ® cpc 250 system connected to an armen ® ls - 5600 collector . this is a semipreparative system into which up to 6 g of crude product can be injected . the products are separated according to their partition coefficient in a given mixture of biphasic solvents . when the heavy phase is held stationary as the mobile phase is continuously injected , this is called ascending mode . the reverse is called descending mode . the system is equipped with a uv - visible detector . as for solanidine , the purification is carried out in ascending mode in a biphasic mixture of h 2 o / buoh / acoet ( 50 : 7 . 5 : 42 . 5 ). centrifugation is carried out at 3000 rpm . the specific optical rotation measurements are made at a temperature of 20 ° c . using the perkin - elmer 343 polarimeter , which emits polarized light at a wavelength ( a ) of 549 nm ( sodium d line ). concentrations c are expressed in grams per 100 ml of solvent . melting points were measured using a büchi 535 automatic apparatus with a maximum temperature of 275 ° c . infrared spectrometry analyses are carried out on a shimadzu ® ftir - 84005 spectrometer . measurements are recorded using the atr technique with the ir solution software and the values of the bands obtained are expressed in cm − 1 . low - resolution mass spectrometry analyses are carried out on a single - quadrupole device ( micromass zq , waters ) having an electrospray ionization source ( z - spray ). this apparatus allows the use of positive - or negative - ion mode . the capillary voltage is 3 . 5 kv and the cone voltage was varied between | 20 | and | 120 | v . the source and desolvation temperatures are 80 and 150 ° c ., respectively . the desolvation / nebulization gas is nitrogen . high - resolution mass spectrometry ( hrms ) analyses are performed on a hybrid quadrupole time - of - flight mass spectrometer ( micromass q - tof ultima global , waters ) equipped with an electrospray ionization source . the source and desolvation temperatures are 80 and 120 ° c ., respectively . the gas used for nebulization and desolvation is nitrogen at flow rates of 20 and 500 i / h , respectively . the capillary voltage is 3 . 5 kv and the cone voltage was varied between 100 and 250 v . before any measurement of exact mass , a calibration with orthophosphoric acid is carried out . since the precision of the q - tof measurement of exact mass is below 5 ppm , it is possible to access the elemental composition of the molecules . the 1 h nmr and 13 c nmr spectra are recorded using two nmr spectrometers . the first is a bruker avance 300 spectrometer . the 1 h nmr spectra are recorded at 300 mhz and the 13 c nmr spectra at 75 mhz . a 5 mm qnp probe is used . the second is a bruker avance 600 spectrometer . in this case , the 1 h nmr spectra are recorded at 600 mhz and the 13 c nmr spectra at 150 mhz . a 5 mm txi probe is used . all the experiments were carried out at a temperature of about 25 ° c . in deuterated solvent , which also serves as a reference , except for d 2 o where a drop of methanol is used as the reference for 13 c nmr ( see table 1 below ). chemical shifts are given in ppm . coupling constants are expressed in hertz . the nmr spectra are processed using topspin or mestrenova . 1 , 2 , 3 , 4 , 6 - penta - β - acetyl - 6 - d - glucopyranose ( 25 . 62 mmol , 10 . 0 g ) is dissolved in anhydrous dichloromethane ( 3 . 12 mol , 200 ml ). the reaction medium is then placed under an inert atmosphere . propargylic alcohol ( 30 . 72 mmol , 1 . 82 ml ) and bf 3 . et 2 o ( 102 . 48 mmol , 12 . 64 ml ) are added . the mixture is stirred for 2 hours , still under an inert atmosphere and at room temperature . potassium carbonate ( 38 . 43 mmol , 5 . 31 g ) is added and the mixture is stirred for 30 minutes . the reaction medium is filtered through sintered glass and the yellow filtrate collected is washed with 2 × 200 ml of distilled water . the aqueous phases are combined and extracted with 2 × 100 ml of dichloromethane . the organic phases are combined and dried over mgso 4 . the solvent is evaporated under reduced pressure . the solid obtained is dissolved in dichloromethane and then crystallized by adding cyclohexane until cloudy . the mixture is stirred for 20 minutes and then filtered through sintered glass . the crystallization is repeated twice . the white solid obtained is dried in a desiccator overnight . compound 2 is thus obtained with a yield of 84 % ( 8 . 3 g ). ft - ir ( atr in cm − 1 ): 3273 ( uc ≡ h ), 1753 - 1732 ( uc ═ o ), 1232 - 1207 ( uc — o ), 1037 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 5 . 19 ( t , 1h , 3 j 3 , 2 = 3 j 3 , 4 = 9 . 6 hz , h 3 ), 5 . 05 ( t , 1h , 3 j 4 , 3 = 3 j 4 , 5 = 9 . 6 hz , h 4 ), 4 . 96 ( dd , 1h , 3 j 2 , 3 = 9 . 6 hz , 3 j 2 , 1 = 7 . 8 hz , h 2 ), 4 . 73 ( d , 1h , 3 j 1 , 2 = 7 . 8 hz , h 1 ), 4 . 32 ( d , 2h , 4 j 1 ′, 1 ′″ , = 2 . 4 hz , h 1 ′ ), 4 . 23 ( dd , 1h , 2 j 6a , 6b = 12 . 3 hz , 3 j 6a , 5 = 4 . 5 hz , h 6a ), 4 . 09 ( dd , 1h , 2 j 6b , 6a = 12 . 3 hz , 3 j 6b , 5 = 2 . 4 hz , h 6b ), 3 . 69 ( ddd , 1h , 3 j 5 , 4 = 9 . 6 hz , 3 j 5 , 6a = 4 . 5 hz , 3 j 5 , 6b = 2 . 4 hz , h 5 ), 2 . 45 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ), 2 . 04 - 1 . 96 ( 4s , 12h , ch 3 co 2 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 170 . 64 - 169 . 42 ( ch 3 c o 2 ), 98 . 16 ( c 1 ), 78 . 16 ( c 1 ″ ), 75 . 59 ( c 1 ′″ ), 72 . 78 ( c 3 ), 71 . 94 ( c 5 ), 70 . 98 ( c 2 ), 68 . 33 ( c 4 ), 61 . 79 ( c 6 ), 55 . 96 ( c 1 ′ ), 20 . 73 - 20 . 61 ( c h 3 co 2 ) compound 2 ( 23 . 0 mmol , 8 . 9 g ) is dissolved in methanol ( 4 . 9 mol , 200 ml ). a solution of sodium ( 20 . 0 mmol , 465 mg ) in methanol ( 4 . 9 mol , 200 ml ) is then added to the reaction medium . the mixture is stirred for 15 hours at room temperature . an ion - exchange resin ( ir - 120 [ h ] + ) is then added to a ph of 5 - 6 . the reaction medium is filtered through sintered glass and the resin is washed with methanol . the solvent is evaporated under reduced pressure and the solid dried in a desiccator overnight . compound 3 is obtained with a yield of 98 % ( 4 . 9 g ). ft - ir ( atr in cm − 1 ): 3289 ( uo — h ), 3236 ( uc ≡ h ), 2874 ( uc — h ), 1365 ( uc — o ), 1026 ( uc — o ) 1 h nmr ( d 2 o , 300 mhz ) δ 4 . 61 ( d , 1h , 3 j 1 , 2 = 8 . 1 hz , h 1 ), 4 . 54 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 15 . 9 hz , 4 j 1 ′ a , 1 ′″ = 2 . 4 hz , h 1 ′ a ), 4 . 48 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 15 . 9 hz , 4 j 1 ′ b , 1 ′″ = 2 . 4 hz , h 1 ′ b ), 3 . 95 ( dd , 1h , 2 j 6a , 6b = 12 . 3 hz , 3 j 6a , 5 = 2 . 2 hz , h 6a ), 3 . 76 ( dd , 1h , 2 j 6b , 6a = 12 . 3 hz , 3 j 6b , 5 = 5 . 7 hz , h 6b ), 3 . 50 ( m , 3h , h 3 , h 4 and h 5 ), 3 . 33 ( dd , 1h , 3 j 2 , 1 = 8 . 1 hz , 3 j 2 , 3 = 9 . 0 hz , h 2 ), 2 . 99 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ) 13 c nmr ( d 2 o , 75 mhz ) δ 101 . 09 ( c 1 ), 79 . 45 ( c 1 ″ ), 76 . 98 ( c 1 ′″ ), 76 . 51 ( c 3 , c 4 or c 5 ), 76 . 25 ( c 3 , c 4 or c 5 ), 73 . 42 ( c 2 ), 70 . 10 ( c 3 , c 4 or c 5 ), 61 . 26 ( c 6 ), 57 . 08 ( c 1 ′ ) 1 , 2 , 3 , 4 , 6 - penta - o - acetyl - 8 - d - galactopyranose ( 12 . 81 mmol , 5 . 0 g ) and silver trifluoroacetate ( 19 . 21 mmol , 4 . 28 g ) are placed under an inert atmosphere . anhydrous dichloromethane ( 2 . 34 mol , 150 ml ) is added , followed by propargylic alcohol ( 19 . 21 mmol , 1 . 13 ml ) and tin chloride ( 38 . 43 mmol , 4 . 5 ml ). the solution is stirred under an inert atmosphere at room temperature for 1 . 5 hours . the reaction medium is diluted by adding 400 ml of dichloromethane and then washed successively with 300 ml of saturated nahco 3 solution , 3 × 300 ml of distilled water and finally 300 ml of saturated nacl solution . the organic phase is dried over mgso 4 and the solvents are evaporated under reduced pressure . the yellow syrup obtained is purified by conventional chromatography on silica gel with an acoet / cyclohexane ( 20 : 80 to 40 : 60 ) elution gradient . the residue is dried in a desiccator overnight . compound 5 is thus obtained with a yield of 87 % ( 4 . 3 g ). ft - ir ( atr in cm − 1 ): 3276 ( uc ≡ h ), 1741 ( uc ═ o ), 1212 - 1044 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 5 . 30 ( dd , 1h , 3 j 4 , 3 = 3 . 4 hz , 3 j 4 , 5 = 1 . 0 hz , h 4 ), 5 . 11 ( dd , 1h , 3 j 2 , 3 = 10 . 5 hz , 3 j 2 , 1 = 7 . 9 hz , h 2 ), 4 . 96 ( t , 1h , 3 j 3 , 2 = 10 . 5 hz , 3 j 3 , 4 = 3 . 4 hz , h 3 ), 4 . 65 ( d , 1h , 3 j 1 , 2 = 7 . 9 hz , h 1 ), 4 . 28 ( d , 2h , 4 j 1 ′, 1 ′″ = 2 . 4 hz , h 1 ′ ), 4 . 09 ( dd , 1h , 2 j 6a , 6b = 11 . 2 hz , 3 j 6a , 5 = 6 . 6 hz , h 6a ), 4 . 04 ( dd , 1h , 2 j 6b , 6a = 11 . 2 hz , 3 j 6b , 5 = 6 . 6 hz , h 6b ), 3 . 87 ( dt , 1h , 3 j 5 , 4 = 1 . 0 hz , 3 j 5 , 6 = 6 . 6 hz , h 5 ), 2 . 43 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ), 2 . 06 - 1 . 89 ( 4s , 12h , ch 3 co 2 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 170 . 13 - 169 . 29 ( ch 3 c o 2 ), 98 . 49 ( c 1 ), 78 . 15 ( c 1 ″ ), 75 . 40 ( c 1 ′″ ), 70 . 68 ( c 3 or c 5 ), 70 . 64 ( c 3 or c 5 ), 68 . 36 ( c 2 ), 66 . 88 ( c 4 ), 61 . 07 ( c 6 ), 55 . 72 ( c 1 ′ ), 20 . 58 - 20 . 37 ( c h 3 co 2 ) compound 5 ( 11 . 13 mmol , 4 . 3 g ) is dissolved in methanol ( 2 . 47 mol , 100 ml ). a solution of sodium ( 10 . 0 mmol , 230 mg ) in methanol ( 2 . 47 mol , 100 ml ) is then added to the reaction medium . the mixture is stirred for 15 hours at room temperature . an ion - exchange resin ( ir - 120 [ h + ]) is added to a ph of 5 - 6 . the reaction medium is filtered through sintered glass and the resin is washed with methanol . the solvents are evaporated under reduced pressure and the residue obtained is dried in a desiccator overnight . compound 6 is obtained with a yield of 91 % ( 2 . 2 g ). ft - ir ( atr in cm − 1 ): 3257 ( uo — h ), 3234 ( uc ≡ h ), 2938 - 2874 ( uc — h ), 1365 - 1294 ( uo — h ), 1044 - 1026 ( uc — o ) 1 h nmr ( d 2 o , 300 mhz ) δ 4 . 59 ( d , 1h , 3 j 1 , 2 = 7 . 8 hz , h 1 ), 4 . 53 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 15 . 9 hz , 4 j 1 ′ a , 1 ′″ = 2 . 5 hz , h 1 ′ a ), 4 . 46 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 15 . 9 hz , 4 j 1 ′ b , 1 ′″ = 2 . 5 hz , n 1 ′ b ), 3 . 95 ( dd , 1h , 3 j 5 , 4 = 0 . 3 hz , 3 j 5 , 6 = 3 . 5 hz , h 5 ), 3 . 78 ( m , 3h , h 6a , h 6b , h 4 ), 3 . 68 ( dd , 1h , 3 j 3 , 2 = 9 . 9 hz , 3 j 3 , 4 = 3 . 5 hz , h 3 ), 3 . 55 ( dd , 1h , 3 j 2 , 1 = 7 . 8 hz , 3 j 2 , 3 = 9 . 9 hz , h 2 ), 2 . 93 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 5 hz , h 1 ′″ ) 13 c nmr ( d 2 o , 75 mhz ) δ 101 . 13 ( c 1 ), 78 . 99 ( c 1 ″ ), 76 . 30 ( c ′″ ), 75 . 26 ( c 4 ), 72 . 75 ( c 3 ), 70 . 55 ( c 2 ), 68 . 60 ( c 5 ), 60 . 95 ( c 6 ), 56 . 51 ( c 1 ′ ) l - rhamnose ( 109 . 0 mmol , 20 . 0 g ) and acetic anhydride ( 0 . 85 mol , 80 ml ) are dissolved in pyridine ( 0 . 99 mol , 80 ml ). the reaction medium is stirred for 15 hours at room temperature . the solvent is evaporated under reduced pressure . the residue obtained is dissolved in 250 ml of ethyl acetate and washed with 2 × 100 ml of distilled water , 2 × 100 ml of saturated nahco 3 solution and 1 × 100 ml of saturated nacl solution . the organic phase is dried over mgso 4 and then filtered through sintered glass . the solvents are evaporated under reduced pressure and then coevaporated with 5 × 100 ml of toluene . the syrup obtained is dried in a desiccator overnight . compound 8 is thus obtained in an a / β mixture ( 86 : 14 ) and with a yield of 98 % ( 35 . 1 g ). ft - ir ( atr in cm − 1 ) 2956 ( uc — h ), 1744 ( uc ═ o ), 1368 ( uc — o ), 1209 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) α diastereoisomer : δ 5 . 96 ( d , 1h , 3 j 1 , 2 = 1 . 9 hz , h 1 ), 5 . 27 ( dd , 1h , 3 j 3 , 2 = 3 . 5 hz , 3 j 3 , 4 = 10 . 0 hz , h 3 ), 5 . 20 ( dd , 1h , 3 j 2 , 3 = 3 . 5 hz , 3 j 2 , 1 = 1 . 9 hz , h 2 ), 5 . 06 ( dd , 1h , 3 j 4 , 3 = 10 . 0 hz , 3 j 4 , 5 = 10 . 0 hz , h 4 ), 3 . 89 ( dd , 1h , 3 j 5 , 4 = 10 . 0 hz , 3 j 5 , 6 = 6 . 3 hz , h 5 ), 2 . 11 - 1 . 94 ( 4s , 12h , ch 3 co 2 ), 1 . 18 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h 6 ) 13 c nmr ( cdcl 3 , 75 mhz ) α diastereoisomer : δ 170 . 00 - 168 . 30 ( ch 3 c o 2 ), 90 . 63 ( c 1 ), 70 . 46 ( c 4 ), 68 . 78 ( c 2 , c 3 or c 5 ), 68 . 70 ( c 2 , c 3 or c 5 ), 68 . 64 ( c 2 , c 3 or c 5 ), 20 . 85 - 20 . 62 ( c h 3 co 2 ), 17 . 42 ( c 6 ) compound 8 ( 11 . 14 mmol , 3 . 8 g ) is placed under an inert atmosphere and dissolved in anhydrous dichloromethane ( 0 . 78 mol , 50 ml ). propargylic alcohol ( 13 . 72 mmol , 0 . 81 ml ) is added to the reaction medium as well as boron trifluoride diethyl etherate at 0 ° c . ( 45 . 74 mmol , 5 . 65 ml ). the mixture is stirred for 15 hours at room temperature . potassium carbonate ( 17 . 15 mmol , 2 . 37 g ) is added and the mixture is stirred for 30 minutes . the reaction medium is filtered through sintered glass . the collected yellow filtrate is concentrated under reduced pressure , diluted with 100 ml of dichloromethane and washed with 2 × 100 ml of distilled water . the aqueous phases are combined and extracted with 2 × 50 ml of dichloromethane . the organic phases are combined and dried over mgso 4 . the solvents are evaporated under reduced pressure . a brown oil is collected , which is purified by automated flash chromatography ( cyclohexane / acoet : 100 : 0 to 60 : 40 over 20 minutes ). the solid is dried in a desiccator overnight . compound 9 is thus obtained with a yield of 79 % ( 2 . 88 g ). ft - ir ( atr in cm − 1 ): 3293 ( uc ≡ h ), 2988 - 2941 ( uc — h ), 1742 ( uc ═ o ), 1220 - 1212 ( uc — o ), 1054 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 5 . 33 ( dd , 1h , 3 j 3 , 2 = 3 . 9 hz , 3 j 3 , 4 = 9 . 7 hz , h 3 ), 5 . 18 ( dd , 1h , 3 j 2 , 3 = 3 . 9 hz , 3 j 2 , 1 = 1 . 0 hz , h 2 ), 4 . 99 ( t , 1h , 3 j 4 , 3 = 9 . 7 hz , h 4 ), 4 . 86 ( dd , 1h , 3 j 1 , 2 = 1 . 0 hz , h 1 ), 4 . 18 ( d , 2h , 4 j 1 ′, 1 ′″ = 2 . 4 hz , h 1 ′ ), 3 . 82 ( dq , 1h , 3 j 5 , 4 = 9 . 7 hz , 3 j 5 , 6 = 6 . 3 hz , h 5 ), 2 . 43 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ), 2 . 07 - 1 . 90 ( 3s , 9h , ch 3 co 2 ), 1 . 15 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h 6 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 170 . 02 - 169 . 97 ( ch 3 c o 2 ), 96 . 11 ( c 1 ), 78 . 27 ( c 1 ″ ), 75 . 35 ( c 1 ′″ ), 70 . 95 ( c 4 ), 69 . 66 ( c 2 ), 69 . 01 ( c 3 ), 66 . 92 ( c 5 ), 20 . 92 - 20 . 73 ( c h 3 co 2 ), 17 . 32 ( c 6 ) compound 9 ( 16 . 5 mmol , 5 . 41 g ) is dissolved in methanol ( 2 . 47 mol , 100 ml ). a solution of sodium ( 10 . 0 mmol , 230 mg ) in methanol ( 2 . 47 mol , 100 ml ) is then added to the reaction medium . the solution is stirred for 15 hours at room temperature . an ion - exchange resin ( ir - 120 [ h + ]) is added to a ph of 5 - 6 . the mixture is filtered through sintered glass and the resin is washed with methanol . the solvents are evaporated under reduced pressure and the residue obtained is dried in a desiccator overnight . compound 10 is obtained with a yield of 90 % ( 3 . 0 g ). ft - ir ( atr in cm − 1 ): 3543 - 3336 ( uo — h ), 3283 ( uc ≡ h ), 2946 - 2909 ( uc — h ), 2119 ( uc ≡ c ), 1446 - 1228 ( uo — h ), 1129 - 1048 ( uc — o ) 1 h nmr ( d 2 o , 300 mhz ) δ 4 . 98 ( d , 1h , 3 j 1 , 2 = 1 . 5 hz , h 1 ), 4 . 37 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 16 . 1 hz , 4 j 1 ′ a , 1 ′ b = 2 . 4 hz , h 1 ′ a ), 4 . 31 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 16 . 1 hz , 4 j 1 ′ b , 1 ′″ = 2 . 4 hz , h 1 ′ b ), 3 . 96 ( dd , 1h , 3 j 2 , 1 = 1 . 5 hz , 3 j 2 , 3 = 3 . 4 hz , h 2 ), 3 . 77 ( dd , 1h , 3 j 3 , 2 = 3 . 4 hz , 3 j 3 , 4 = 9 . 6 hz , h 3 ), 3 . 74 ( dd , 1h , 3 j 5 , 4 = 9 . 6 hz , 3 j 5 , 6 = 6 . 3 hz , h 5 ), 3 . 47 ( dd , 1h , 3 j 4 , 3 = 9 . 6 hz , 3 j 4 , 5 = 9 . 6 hz , h 4 ), 2 . 94 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ), 1 . 31 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h 6 ) 13 c nmr ( d 2 o , 75 mhz ) δ 99 . 82 ( c 1 ), 79 . 79 ( c 1 ″ ), 77 . 09 ( c 1 ′″ ), 72 . 85 ( c 4 ), 71 . 10 ( c 2 ), 70 . 94 ( c 3 ), 70 . 02 ( c 5 ), 55 . 64 ( c 1 ′ ), 17 . 47 ( c 6 ) compound 8 ( 5 . 12 mmol , 1 . 68 g ) and thiourea ( 5 . 64 mmol , 0 . 43 g ) are placed under an inert atmosphere and dissolved in anhydrous acetonitrile ( 0 . 19 mol , 10 ml ). bf 3 . et 2 o ( 10 . 76 mmol , 1 . 33 ml ) is added to the reaction medium . the solution is refluxed for 30 minutes . the reaction medium is cooled to room temperature and pyridine is added ( 10 . 76 mmol , 0 . 90 ml ). the solvents are evaporated under vacuum . the syrup obtained is diluted in 15 ml of isopropanol and the mixture is stirred rapidly at room temperature to crystallize the pyridinium - boron complex . the solid is filtered through sintered glass and the filtrate concentrated under reduced pressure . the residue obtained is dissolved in 15 ml of ethanol and the mixture is stirred rapidly at room temperature . the solid obtained is filtered through sintered glass , washed with ethanol and dried in a desiccator overnight . it consists of 80 % by mass of compound 17 and 20 % by mass of boron trifluoride - pyridinium salt . the yield is 85 % ( 1 . 52 g ). empirical formula : c 13 h 21 n 2 o 7 s ft - ir ( atr in cm − 1 ) 3389 - 3235 ( un — h ), 1734 ( uc ═ o ), 1659 ( un — h ), 1242 - 1066 ( uc — o ) 1 h nmr ( c 2 d 6 so , 300 mhz ) δ 9 . 31 ( s , 2h , nh 2 ), 9 . 25 ( s , 2h , nh 2 ), 6 . 21 ( d , 1h , 3 j 1 , 2 = 1 . 2 hz , h 1 ), 5 . 37 ( dd , 1h , 3 j 2 , 1 = 1 . 6 hz , 3 j 2 , 3 = 2 . 9 hz , h 2 ), 4 . 99 ( m , 2h , h 3 and h 4 ), 4 . 51 ( m , 1h , h 5 ), 2 . 14 - 1 . 96 ( 3s , 9h , ch 3 co 2 ), 1 . 19 ( d , 3h , 3 j 6 , 5 = 6 . 2 hz , h 6b ) 13 c nmr ( c 2 d 6 so , 75 mhz ) δ 169 . 72 - 169 . 36 ( ch 3 c o 2 ), 165 . 15 ( s c ( nh 2 ) 2 ), 81 . 67 ( c 1 ), 69 . 59 ( c 3 or c 4 ), 69 . 12 ( c 2 and c 5 ), 68 . 43 ( c 3 or c 4 ), 20 . 47 - 20 . 37 ( c h 3 co 2 ), 17 . 11 ( c 6 ) compound 17 ( 3 . 22 mmol , 1 . 12 g ) is placed under an inert atmosphere and dissolved in anhydrous acetonitrile ( 38 . 30 mmol , 20 ml ). triethylamine ( 9 . 97 mmol , 1 . 39 ml ) is added followed by 80 % propargyl bromide in toluene ( 3 . 54 mmol , 0 . 39 ml ). the reaction medium is stirred for 1 hour at room temperature . the solvent is evaporated under vacuum and the syrup obtained is diluted in 30 ml of toluene . the organic phase is washed with 3 × 30 ml of distilled water . the aqueous phases are combined and extracted with 50 ml of toluene . the organic phases are combined and dried over mgso 4 . the solvent is evaporated under reduced pressure . the obtained yellowish syrup is purified by conventional chromatography on silica gel with an acoet / cyclohexane ( 20 : 80 to 40 : 60 ) elution gradient . the solid is dried in a desiccator overnight . compound 18 is obtained with a yield of 73 % ( 0 . 81 g ). ft - ir ( atr in cm − 1 ): 3293 ( uc ≡ h ), 2985 ( uc — h ), 1742 - 1939 ( uc ═ o ), 1213 - 1039 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 5 . 39 ( d , 1h , 3 j 1 , 2 = 1 . 3 hz , h 1 ), 5 . 37 ( dd , 1h , 3 j 2 , 3 = 3 . 2 hz , 3 j 2 , 1 = 1 . 3 hz , h 2 ), 5 . 18 ( dd , 1h , 3 j 3 , 2 = 3 . 2 hz , 3 j 3 , 4 = 10 . 0 hz , h 3 ), 5 . 10 ( dd , 1h , 3 j 4 , 3 = 10 . 0 hz , 3 j 4 , 5 = 9 . 2 hz , h 4 ), 4 . 18 ( dq , 1h , 3 j 5 , 4 = 9 . 2 hz , 3 j 5 , 6 = 6 . 2 hz , h 5 ), 3 . 39 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 16 . 8 hz , 4 j 1 ′ a , 1 ′″ = 2 . 6 hz , h 1 ′ a ), 3 . 22 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 16 . 8 hz , 4 j 1 ′ b , 1 ′″ = 2 . 6 hz , h 1 ′ b ), 2 . 25 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 6 hz , h 1 ′″ ), 2 . 15 - 1 . 96 ( 3s , 9h , ch 3 co 2 ), 1 . 23 ( d , 3h , 3 j 6 , 5 = 6 . 2 hz , h 6 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 169 . 86 - 169 . 79 ( ch 3 c o 2 ), 81 . 35 ( c 1 ), 78 . 80 ( c 1 ″ ), 71 . 92 ( c 1 ′″ ), 71 . 06 ( c 4 ), 70 . 79 ( c 2 ), 69 . 54 ( c 3 ), 67 . 45 ( c 5 ), 20 . 87 - 20 . 61 ( c h 3 co 2 ), 18 . 24 ( c 1 ′ ), 17 . 31 ( c 6 ) compound 18 ( 3 . 48 mmol , 1 . 20 g ) is dissolved in methanol ( 1 . 23 mol , 50 ml ). a solution of sodium ( 5 . 0 mmol , 115 mg ) in methanol ( 1 . 23 mol , 50 ml ) is added to the reaction medium . the mixture is stirred for 15 hours at room temperature . ion - exchange resin ir - 120 [ h + ] is added to a ph of 5 - 6 . the reaction medium is filtered through sintered glass and the resin is washed with methanol . the solvent is evaporated under reduced pressure . the syrup obtained is dried in a desiccator overnight . compound 19 is thus obtained with a yield of 88 % ( 0 . 67 g ). ft - ir ( atr in cm − 1 ): 3385 ( uo — h ), 3288 ( uc ≡ h ), 2976 - 2933 ( uc — h ), 1058 ( uc — o ) 1 h nmr ( d 2 o , 300 mhz ) δ 5 . 42 ( s , 1h , h 1 ), 4 . 05 ( dd , 1h , 3 j 2 , 3 = 3 . 5 hz , 3 j 2 , 1 = 1 . 5 hz , h 2 ), 4 . 00 ( dq , 1h , 3 j 5 , 4 = 3 . 4 hz , 3 j 5 , 6 = 6 . 3 hz , h 5 ), 3 . 71 ( dd , 1h , 3 j 3 , 2 = 3 . 5 hz , 3 j 3 , 4 = 9 . 7 hz , h 3 ), 3 . 47 ( dd , 1h , 3 j 4 , 3 = 9 . 7 hz , 3 j 4 , 5 = 3 . 4 hz , h 4 ), 3 . 45 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 17 . 1 hz , 4 j 1 ′ a , 1 ′″ = 2 . 6 hz , h 1 ′ a ), 3 . 34 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 17 . 1 hz , 4 j 1 ′ b , 1 ′″ = 2 . 6 hz , h 1 ′ b ), 2 . 67 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 6 hz , h 1 ′″ ), 1 . 29 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h 6 ) 13 c nmr ( d 2 o , 75 mhz ) δ 84 . 65 ( c 1 ), 80 . 83 ( c 1 ″ ), 73 . 06 ( c 1 ′″ ), 72 . 95 ( c 4 ), 72 . 13 ( c 2 ), 71 . 62 ( c 3 ), 70 . 13 ( c 5 ), 18 . 51 ( c 1 ′ ), 17 . 33 ( c 6 ) compound 6 ( 0 . 92 mmol , 200 mg ) is dissolved in pyridine ( 30 . 9 mmol , 2 . 5 ml ) and cooled to 0 ° c . benzoyl chloride ( 3 . 30 mmol , 0 . 38 ml ) is then added and the solution is stirred for 15 hours at room temperature . the reaction is quenched by adding 4 ml of distilled water . the reaction medium is diluted with 20 ml of toluene and then washed successively with 20 ml of saturated nahco 3 solution , 20 ml of 1 m hcl solution and finally 20 ml of distilled water . the organic phase is dried over mgso 4 and the solvents are evaporated under reduced pressure . the residue is purified by means of automated flash chromatography ( cyclohexane / acoet : 100 : 0 to 80 : 20 over 30 minutes ). the solid is dried in a desiccator overnight . compound 25 is obtained with a yield of 70 % ( 342 mg ). ft - ir ( atr in cm − 1 ): 3458 ( uo — h ), 2971 - 2927 ( uc — h ), 1722 - 1704 ( uc ═ o ), 1318 - 1261 ( uc — o ), 1111 - 1072 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 8 . 05 - 7 . 96 ( m , 6h , ch ═ ch ), 7 . 60 - 7 . 30 ( m , 9h , ch ═ ch ), 5 . 82 ( dd , 1h , 3 j 2 , 1 = 8 . 0 hz , 3 j 2 , 3 = 10 . 3 hz , h 2 ), 5 . 40 ( dd , 1h , 3 j 3 , 2 = 10 . 3 hz , 3 j 3 , 4 = 3 . 2 hz , h 3 ), 5 . 04 ( d , 1h , 3 j 1 , 2 = 8 . 0 hz , h 1 ), 4 . 70 ( dd , 1h , 2 j 6a , 6b = 11 . 4 hz , 3 j 6a , 5 = 6 . 4 hz , h 6a ), 4 . 70 ( dd , 1h , 2 j 6b , 6a = 11 . 4 hz , 3 j 6b , 5 = 6 . 4 hz , h 6b ), 4 . 47 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 16 . 0 hz , 4 j 1 ′ a , 1 ″ = 2 . 3 hz , h 1 ′ a ), 4 . 41 ( d , 1h , 3 j 4 , 3 = 3 . 2 hz , h 4 ), 4 . 37 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 16 . 0 hz , 4 j 1 ′ b , 1 ′″ = 2 . 3 hz , h 1 ′ b ), 4 . 13 ( t , 1h , 3 j 5 , 6 = 6 . 4 hz , h 5 ), 2 . 95 ( s , 1h , oh ), 2 . 38 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 3 hz , h 1 ′″ ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 166 . 57 - 165 . 59 ( phco 2 ), 133 . 56 - 133 . 21 ( ch ═ ch ), 129 . 98 - 128 . 36 ( ch ═ ch ), 98 . 83 ( c 1 ), 78 . 44 ( c 1 ″ ), 75 . 44 ( c 1 ′″ ), 74 . 32 ( c 3 ), 72 . 70 ( c 5 ), 69 . 40 ( c 2 ), 67 . 35 ( c 4 ), 62 . 96 ( c 6 ), 55 . 87 ( c 1 ′ ) compound 25 ( 1 . 22 mmol , 650 mg ) is placed under an inert atmosphere and dissolved in anhydrous dichloromethane ( 0 . 14 mol , 9 ml ). the reaction medium is placed at − 20 ° c . and pyridine ( 9 . 8 mmol , 0 . 80 ml ) is added followed by the addition of tf 2 o ( 2 . 5 mmol , 0 . 42 ml ). the mixture is stirred for 2 hours while rising from − 20 ° c . to 10 ° c . the solution is diluted with 20 ml of dichloromethane and is washed successively with 30 ml of 1 m hcl solution , 30 ml of saturated nahco 3 solution and 30 ml of saturated nacl solution . the organic phase is dried over mgso 4 . a yellow syrup is directly obtained and placed under an inert atmosphere . anhydrous acetonitrile ( 0 . 19 mol , 10 ml ), triethylamine ( 4 . 4 mmol , 0 . 60 ml ) and finally compound 17 ( 1 . 47 mmol , 647 mg ) are added . the reaction medium is stirred for 2 hours at room temperature . the solvent is evaporated under reduced pressure and the residue obtained is diluted with 30 ml of toluene . the organic phase is washed with 2 × 30 ml of distilled water . the aqueous phases are combined and extracted with 2 × 30 ml of toluene . the organic phases are combined and dried over mgso 4 . the solvent is evaporated under reduced pressure . the syrup is purified by means of automated flash chromatography ( cyclohexane / acoet : 100 : 0 to 75 : 25 over 20 minutes ). the residue is dried in a desiccator overnight . compound 27 is obtained with a yield of 60 % ( 599 mg ). hrms : 841 . 2150 ( 841 . 2142 calculated for c 42 h 42 o 15 sna ) ft - ir ( atr in cm − 1 ): 3286 ( uc ≡ h ), 2972 - 2927 ( uc — h ), 1722 - 1704 ( uc ═ o ), 1318 - 1261 ( uc — o ), 1139 - 1028 ( uc — o ), 718 ( uc — o ) 1 h nmr ( cdcl 3 , 600 mhz ): 8 . 08 ( m , 2h , ch ═ ch ), 7 . 95 ( m , 4h , ch ═ ch ), 7 . 60 ( m , 1h , ch ═ ch ), 7 . 49 ( m , 4h , ch ═ ch ), 7 . 36 ( m , 4h , ch ═ ch ), 5 . 66 ( dd , 1h , 3 j 3 , 2 = 9 . 5 hz , 3 j 3 , 4 = 11 . 1 hz , h glc3 ), 5 . 46 ( dd , 1h , 3 j 2 , 1 = 8 . 0 hz , 3 j 2 , 3 = 9 . 5 hz , h glc2 ), 5 . 45 ( d , 1h , 3 j 1 , 2 = 1 . 3 hz , h rha1 ), 5 . 24 ( dd , 1h , 3 j 2 , 1 = 1 . 3 hz , 3 j 2 , 3 = 2 . 9 hz , h rha2 ), 5 . 03 ( d , 1h , 3 j 1 , 2 = 8 . 0 hz , h glc1 ), 4 . 96 ( dd , 1h , 3 j 3 , 4 = 10 . 0 hz , 3 j 3 , 2 = 2 . 9 hz , h rha3 ), 4 . 95 ( d , 1h , j = 7 . 9 hz , h rha4 ), 4 . 92 ( dd , 1h , 2 j 6a , 6b = 12 . 1 hz , 3 j 6a , 5 = 2 . 3 hz , h glc6a ), 4 . 65 ( dd , 1h , 2 j 6b , 6a = 12 . 1 hz , 3 j 6b , 5 = 4 . 4 hz , h glc6b ), 4 . 40 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 16 . 0 hz , 4 j 1 ′ a , 1 ′″ = 2 . 4 hz , h glc1 ′ a ), 4 . 33 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 16 . 0 hz , 4 j 1 ′ b , 1 ′″ = 2 . 4 hz , h glc1 ′ b ), 4 . 07 ( ddd , 1h , 3 j 5 , 4 = 11 . 1 hz , 3 j 5 , 6a = 2 . 3 hz , 3 j 5 , 6b = 4 . 4 hz , h glc5 ), 3 . 92 ( dq , 1h , 3 j 5 , 4 = 2 . 0 hz , 3 j 5 , 6 = 6 . 2 hz , h rha5 ), 3 . 36 ( t , 1h , 3 j 4 , 3 = 11 . 1 hz , 3 j 4 , 5 = 11 . 1 hz , h glc4 ), 2 . 39 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h glc1 ′″ ), 1 . 99 - 1 . 89 ( 3s , 9h , ch 3 co 2 ), 0 . 96 ( d , 3h , 3 j 6 , 5 = 6 . 2 hz h rha6 ) 13 c nmr ( cdcl 3 , 150 mhz ): 169 . 66 - 169 . 49 ( ch 3 c o 2 ), 165 . 76 - 165 . 23 ( phco 2 ), 133 . 22 - 133 . 16 ( ch ═ ch ), 129 . 84 - 128 . 23 ( ch ═ ch ), 98 . 04 ( c glc1 ), 81 . 12 ( c rha1 ), 78 . 09 ( c glc1 ″ ), 75 . 66 ( c glc1 ′″ ), 74 . 64 ( c glc5 ), 72 . 49 ( c glc2 ), 71 . 18 ( c glc3 ), 70 . 84 ( c rha2 ), 70 . 53 ( c rha3 or c rha4 ), 69 . 01 ( c rha3 or c rha4 ), 67 . 77 ( c rha5 ), 63 . 51 ( c glc6 ), 55 . 72 ( c glc1 ′ ), 46 . 06 ( c glc4 ), 20 . 55 - 20 . 49 ( c h 3 co 2 ), 17 . 02 ( c rha6 ) compound 27 ( 0 . 60 mmol , 484 mg ) is dissolved in methanol ( 0 . 37 mol , 15 ml ). a solution of sodium ( 1 . 25 mmol , 29 mg ) in methanol ( 0 . 25 mol , 10 ml ) is added to the reaction medium . the solution is stirred for 15 hours at room temperature . acid resin ( ir - 120 [ h + ]) is added to a ph of 5 - 6 . the mixture is filtered through sintered glass and the resin is washed with methanol . the solvent is evaporated under vacuum and the residue is purified by means of automated flash chromatography ( ch 2 cl 2 / meoh : 100 : 0 to 75 : 25 over 30 minutes ). the solid obtained is dried in a desiccator overnight . compound 28 is obtained with a yield of 88 % ( 197 mg ). hrms : 403 . 1031 ( 403 . 1039 calculated for c 15 h 24 o 9 sna ) ft - ir ( atr in cm − 1 ): 3398 ( uo — h ), 2972 - 2900 ( uc — h ), 1056 ( uc — o ) 1 h nmr ( cdcl 3 , 600 mhz ): 5 . 31 ( d , 1h , 3 j 1 , 2 = 1 . 2 hz , h rha1 ), 4 . 63 ( d , 1h , 3 j 1 , 2 = 8 . 1 hz , h glc1 ), 4 . 50 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 15 . 9 hz , 4 j 1 ′ a , 1 ′″ = 2 . 3 hz , h glc1 ′ a ), 4 . 46 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 15 . 9 hz , 4 j 1 ′ b , 1 ′″ = 2 . 3 hz , h glc1 ′ b ), 4 . 13 ( dq , 1h , 3 j 5 , 4 = 9 . 6 hz , 3 j 5 , 6 = 6 . 3 hz , h rha5 ), 4 . 11 ( dd , 1h , 3 j 2 , 1 = 1 . 7 hz , 3 j 2 , 3 = 3 . 3 hz , h rha2 ), 4 . 08 ( dd , 1h , 2 j 6a , 6b = 12 . 2 hz , 3 j 6a , 5 = 2 . 0 hz , h glc6a ), 3 . 90 ( dd , 1h , 2 j 6b , 6a = 12 . 2 hz , 3 j 6b , 5 = 5 . 2 hz , h glc6b ), 3 . 72 ( dd , 1h , 3 j 3 , 4 = 9 . 6 hz , 3 j 3 , 2 = 3 . 3 hz , h rha3 ), 3 . 69 ( ddd , 1h , 3 j 5 , 4 = 10 . 9 hz , 3 j 5 , 6a = 2 . 0 hz , 3 j 5 , 6b = 5 . 2 hz , h glc5 ), 3 . 61 ( dd , 1h , 3 j 3 , 2 = 9 . 1 hz , 3 j 3 , 4 = 10 . 9 hz , h glc3 ), 3 . 49 ( t , 1h , 3 j 4 , 3 = 9 . 6 hz , 3 j 4 , 5 = 9 . 6 hz , h rha4 ), 3 . 34 ( t , 1h , 3 j 2 , 3 = 8 . 5 hz , 3 j 2 , 1 = 8 . 5 hz , h glc2 ), 2 . 93 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 3 hz , h glc1 ′″ ), 2 . 78 ( t , 1h , 3 j 4 , 3 = 10 . 9 hz , 3 j 4 , 5 = 10 . 9 hz , h glc4 ), 1 . 30 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz h rha6 ) 13 c nmr ( cdcl 3 , 150 mhz ): 100 . 38 ( c glc1 ), 83 . 66 ( c rha1 ), 78 . 93 ( c glc1 ″ ), 76 . 49 ( c glc1 ′″ ), 76 . 43 ( c glc5 ), 74 . 16 ( c glc2 ), 72 . 52 ( c glc3 , c rha2 or c rha4 ), 72 . 28 ( c glc3 , c rha2 or c rha4 ), 72 . 12 ( c glc3 , c rha2 or c rha4 ), 70 . 82 ( c rha3 ), 69 . 68 ( c rha5 ), 61 . 46 ( c glc6 ), 56 . 54 ( c glc1 ′ ), 48 . 02 ( c glc4 ), 16 . 60 ( c rha6 ) a solution of compound 3 ( 4 . 58 mmol , 1 g ) in pyridine ( 98 . 9 mmol , 8 ml ) and is placed at 0 ° c . pivaloyl chloride ( 11 . 45 mmol , 1 . 41 ml ) is then added dropwise . the reaction medium is stirred for 2 . 5 hours at 0 ° c . the solvent is evaporated under reduced pressure and the residue obtained is dissolved in 100 ml of ethyl acetate . the organic phase is washed successively with 100 ml of dilute hcl solution , 100 ml of saturated nahco 3 solution and finally 100 ml of saturated nacl solution . the organic phase is dried over mgso 4 and the solvent is evaporated under vacuum . the residue is purified by conventional chromatography on silica gel with an acoet / cyclohexane ( 10 : 90 to 40 : 60 ) elution gradient . the solid obtained is dried in a desiccator overnight . compound 54 is obtained with a yield of 53 % ( 0 . 94 g ). ft - ir ( atr in cm − 1 ): 3475 ( uo — h ), 3280 ( uc ≡ h ), 2972 - 2874 ( uc — h ), 1716 ( uc ═ o ), 1283 - 1036 ( uc — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 4 . 93 ( t , 1h , 3 j 3 , 2 = 9 . 2 hz , 3 j 3 , 4 = 9 . 2 hz , h 3 ), 4 . 58 ( d , 1h , 3 j 1 , 2 = 7 . 8 hz , h 1 ), 4 . 42 ( dd , 1h , 2 j 6a , 6b = 12 . 0 hz , 3 j 6a , 5 = 2 . 4 hz , h 6a ), 4 . 40 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 15 . 8 hz , 4 j 1 ′ a , 1 ′″ = 2 . 4 hz , h 1 ′ a ), 4 . 34 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 15 . 8 hz , 4 j 1 ′ b , 1 ′″ = 2 . 4 hz , h 1 ′ b ), 4 . 27 ( dd , 1h , 2 j 6b - 6a = 12 . 0 hz , 3 j 6b - 5 = 6 . 1 hz , h 6b ), 3 . 60 ( ddd , 1h , 3 j 5 - 6a = 2 . 4 hz , 3 j 5 - 6b = 6 . 1 hz , 3 j 5 - 4 = 9 . 8 hz , h 5 ), 3 . 50 ( dd , 1h , 3 j 2 , 1 = 7 . 8 hz , 3 j 2 , 3 = 9 . 2 hz , h 2 ), 3 . 47 ( dd , 1h , 3 j 4 , 3 = 9 . 2 hz , 3 j 4 , 5 = 9 . 8 hz , h 4 ), 2 . 48 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 4 hz , h 1 ′″ ), 1 . 23 - 1 . 20 ( 2s , 18h , ( ch 3 ) 3 cco 2 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 180 . 25 - 178 . 90 (( ch 3 ) 3 c c o 2 ), 100 . 31 ( c 1 ), 78 . 46 ( c 1 ″ ), 77 . 72 ( c 3 ), 75 . 71 ( c 1 ′″ ), 74 . 57 ( c 5 ), 72 . 04 ( c 2 ), 69 . 82 ( c 4 ), 63 . 38 ( c 6 ), 55 . 98 ( c 1 ′ ), 39 . 15 - 39 . 00 (( ch 3 ) 3 c co 2 ), 27 . 26 - 27 . 18 (( c h 3 ) 3 cco 2 ) compound 54 ( 1 . 56 mmol , 600 mg ) is dissolved in 5 ml of anhydrous dichloromethane and then added to activated 4 å molecular sieve placed under atmosphere . the reaction medium is placed at − 78 ° c . and bf 3 - et 2 o ( 7 . 02 mmol , 0 . 86 ml ) is added . the solution is stirred for 1 hour at − 78 ° c . finally , compound 53 ( 4 . 68 mmol , 2 . 03 g ) dissolved in 5 ml of anhydrous dichloromethane is added . the reaction mixture is stirred for 15 hours at room temperature . the molecular sieve is filtered through celite and washed with ethyl acetate . the filtrate is concentrated under reduced pressure and the residue obtained is taken up in 20 ml of chloroform . the organic phase is washed with 20 ml of saturated nahco 3 solution and then 20 ml of saturated nacl solution . it is then dried over mgso 4 and the solvent is evaporated under vacuum . the obtained yellowish solid is purified by means of automated normal - phase flash chromatography ( cyclohexane / acoet : 100 : 0 to 0 : 100 over 30 minutes ) or automated reversed - phase flash chromatography ( h 2 o / meoh : 70 : 30 to 0 : 100 over 20 minutes ). the solid obtained is dried in a desiccator overnight . compound 55 is isolated with a yield of 71 % ( 1 . 03 g ). hrms : 953 . 3591 ( 953 . 3630 calculated for c 43 h 62 o 22 na ) ft - ir ( atr in cm − 1 ): 3445 ( uo — h ), 2977 ( uc — h ), 1745 ( uc ═ o ), 1220 - 1042 ( uc — o ) 1 h nmr ( cdcl 3 , 600 mhz ): 5 . 26 ( t , 1h , 3 j 3 , 4 = 3 j 3 , 2 = 7 . 4 hz , h glc3 ), 5 . 23 ( dd , 1h , 3 j 3 , 4 = 10 . 0 hz , 3 j 3 , 2 = 3 . 4 hz , h rha3 ′ ), 5 . 19 ( d , 1h , 3 j 2 , 3 = 3 . 4 hz , h rha2 ′ ), 5 . 18 ( dd , 1h , 3 j 3 , 4 = 10 . 0 hz , 3 j 3 , 2 = 3 . 2 hz , h rha3 ), 5 . 05 ( dd , 1h , 3 j 2 , 1 = 1 . 6 hz , 3 j 2 , 3 = 3 . 2 hz , h rha2 ), 5 . 04 ( dd , 1h , 3 j 4 , 3 = 10 . 0 hz , 3 j 4 , 5 = 10 . 0 hz , h rha4 or h rha4 ′ ), 5 . 01 ( dd , 1h , 3 j 4 , 3 = 10 . 0 hz , 3 j 4 , 5 = 10 . 0 hz , h rha4 or h rha4 ′ ), 4 . 87 ( d , 1h , 3 j 1 , 2 = 1 . 6 hz , h rha1 ), 4 . 81 ( s , 1h , h rha1 ′ ), 4 . 74 ( d , 1h , 3 j 1 , 2 = 7 . 0 hz , h glc1 ), 4 . 48 ( dd , 1h , 2 j 6a , 6b = 12 . 1 hz , 3 j 6a , 5 = 1 . 6 hz , h glc6a ), 4 . 36 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 16 . 0 hz , 4 j 1 ′ a , 1 ′″ = 2 . 3 hz , h glc1 ′ a ), 4 . 33 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 16 . 0 hz , 4 j 1 ′ b , 1 ′″ = 2 . 3 hz , h glc1 ′ b ), 4 . 26 ( dd , 1h , 2 j 6b , 6a = 12 . 1 hz , 3 j 6b , 5 = 4 . 5 hz , h glc6b ), 4 . 21 ( dq , 1h , 3 j 5 , 4 = 10 . 0 hz , 3 j 5 , 6 = 6 . 3 hz , h rha5 or h rha5 ′ ), 3 . 91 ( dq , 1h , 3 j 5 , 4 = 10 . 0 hz , 3 j 5 , 6 = 6 . 3 hz , h rha5 or h rha5 ′ ), 3 . 78 ( m , 2h , h glc4 and h glc5 ), 3 . 59 ( t , 1h , 3 j 2 , 3 = 7 . 4 hz , 3 j 2 , 1 = 7 . 4 hz , h glc2 ), 2 . 49 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 3 hz , h glc1 ′″ ), 2 . 11 - 1 . 94 ( 6s , 18h , ch 3 co 2 ), 1 . 22 ( s , 9h , ( ch 3 ) 3 cco 2 ), 1 . 19 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h rha6 or h rha6 ′ ), 1 . 17 ( s , 9h , ( ch 3 ) 3 cco 2 ), 1 . 15 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz h rha6 or h rha6 ′ ) 13 c nmr ( cdcl 3 , 150 mhz ): 177 . 74 - 176 . 45 (( ch 3 ) 3 c c o 2 ), 170 . 02 - 169 . 53 ( ch 3 c o 2 ), 98 . 11 ( c rha1 ′ ), 98 . 16 ( c glc1 ), 97 . 42 ( c rha1 ), 78 . 02 ( c glc1 ′″ ), 77 . 79 ( c glc2 ), 76 . 56 ( c glc4 or c glc5 ), 75 . 74 ( c glc1 ″ ), 75 . 08 ( c glc3 ), 72 . 32 ( c glc4 or c glc5 ), 70 . 94 ( c rha4 or c rha4 ′ ), 70 . 53 ( c rha4 or c rha4 ′ ), 69 . 98 ( c rha2 or c rha2 ′ ), 69 . 61 ( c rha2 or c rha2 ′ ), 69 . 05 ( c rha3 or c rha3 ′ ), 68 . 69 ( c rha3 or c rha3 ′ ), 67 . 97 ( c rha5 or c rha5 ′ ), 66 . 81 ( c rha5 or c rha5 ′ ), 62 . 40 ( c glc6 ), 55 . 51 ( c glc1 ′ ), 38 . 88 - 38 . 81 (( ch 3 ) 3 c co 2 ), 27 . 15 - 26 . 86 (( c h 3 ) 3 cco 2 ), 20 . 80 - 20 . 67 ( c h 3 co 2 ), 17 . 16 - 17 . 09 ( c rha6 and c rha6 ′ ) compound 55 ( 0 . 81 mmol , 749 mg ) is dissolved in methanol ( 0 . 61 mol , 25 ml ). a solution of sodium ( 25 mmol , 575 mg ) in methanol ( 0 . 61 mol , 25 ml ) is added . the reaction mixture is stirred for 15 hours at room temperature . acid resin ( ir - 120 [ h + ]) is added to a ph of 5 - 6 . the resin is filtered through sintered glass and washed with methanol . the solvent is evaporated under reduced pressure and the residue obtained is purified by means of automated reversed - phase flash chromatography ( h 2 o / meoh : 100 : 0 to 0 : 100 over 20 minutes ). the product is dried in a desiccator overnight . compound 56 is isolated with a yield of 87 % ( 360 mg ). hrms : 533 . 1857 ( 533 . 1846 calculated for c 21 h 34 o 14 na ) ft - ir ( atr in cm − 1 ): 3390 ( uo — h ), 2931 ( uc — h ), 1128 - 1041 ( uc — o ) 1 h nmr ( cdcl 3 , 600 mhz ): 5 . 03 ( d , 1h , 3 j 1 , 2 = 1 . 5 hz , h rha1 ), 4 . 85 ( d , 1h , 3 j 1 , 2 = 1 . 4 hz , h rha1 ′ ), 4 . 71 ( d , 1h , 3 j 1 , 2 = 7 . 9 hz , h glc1 ), 4 . 50 ( dd , 1h , 2 j 1 ′ a , 1 ′ b = 15 . 8 hz , 4 j 1 ′ a , 1 ′″ = 2 . 3 hz , h glc1 ′ a ), 5 . 46 ( dd , 1h , 2 j 1 ′ b , 1 ′ a = 15 . 8 hz , 4 j 1 ′ b , 1 ′″ = 2 . 3 hz , h glc1 ′ b ), 4 . 03 ( m , 4h , h rha2 , h rha2 ′ , h rha5 and h rha5 ′ ), 3 . 89 ( dd , 1h , 2 j 6a , 6b = 12 . 4 hz , 3 j 6a , 5 = 2 . 2 hz , h glc6a ), 3 . 77 ( t , 1h , 3 j 3 , 2 = 3 j 3 , 4 = 9 . 8 hz , h rha3 ), 3 . 76 ( t , 1h , 3 j 3 , 2 = 3 j 3 , 4 = 9 . 8 hz , h rha3 ′ ), 3 . 74 ( m , 2h , h glc3 and h glc6b ), 3 . 59 ( t , 1h , 3 j 4 , 3 = 9 . 5 hz , 3 j 4 , 5 = 9 . 5 hz , h glc4 ), 3 . 51 ( ddd , 1h , 3 j 5 , 4 = 9 . 5 hz , 3 j 5 , 6a = 2 . 2 hz , 3 j 5 , 6b = 4 . 6 hz , h glc5 ), 3 . 47 ( t , 1h , 3 j 4 , 3 = 3 j 4 , 5 = 9 . 8 hz , h rha4 ), 3 . 46 ( t , 1h , 3 j 4 , 3 = 3 j 4 , 3 = 9 . 8 hz , h rha4 ′ ), 3 . 38 ( dd , 1h , 3 j 2 , 1 = 7 . 9 hz , 3 j 2 , 3 = 9 . 0 hz , h glc2 ), 2 . 94 ( t , 1h , 4 j 1 ′″, 1 ′ = 2 . 3 hz , h glc1 ′″ ), 1 . 29 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h rha6 ), 1 . 26 ( d , 3h , 3 j 6 , 5 = 6 . 3 hz , h rha6 ′ ) 13 c nmr ( cdcl 3 , 150 mhz ): 101 . 78 ( c rha1 ), 101 . 02 ( c rha1 ′ ), 99 . 34 ( c glc1 ), 80 . 19 ( c glc2 ), 78 . 84 ( c glc1 ″ ), 77 . 05 ( c glc4 ), 76 . 59 ( c glc1 ′″ ), 75 . 15 ( c glc5 ), 74 . 93 ( c glc3 ), 72 . 08 ( c rha4 or c rha4 ′ ), 72 . 00 ( c rha4 or c rha4 ′ ), 70 . 46 ( c rha2 , c rha2 ′ , c rha3 or c rha3 ′ ), 70 . 33 ( c rha2 , c rha2 ′ , c rha3 or c rha3 ′ ), 70 . 29 ( c rha2 , c rha2 ′ , c rha3 or c rha3 ′ ), 70 . 27 ( c rha2 , c rha2 ′ , c rha3 or c rha3 ′ ), 69 . 12 ( c rha5 or c rha5 ′ ), 69 . 04 ( c rha5 or c rha5 ′ ), 60 . 18 ( c glc6 ), 56 . 62 ( c glc1 ′ ), 16 . 76 - 16 . 57 ( c rha6 and c rha6 ′ ) 3 - chloropropan - 1 - ol ( 0 . 11 mol , 10 g ) is dissolved in distilled water ( 0 . 81 mol , 45 ml ). sodium azide ( 0 . 21 mmol , 13 . 78 g ) is added and the reaction medium is stirred for 15 hours at 80 ° c . the reaction medium is washed with 3 × 50 ml of diethyl ether . the organic phases are combined and dried over mgso 4 . because the product is volatile , the solvent is evaporated under reduced pressure at mild temperature ( 15 ° c .). compound 66 is obtained with a yield of 99 % ( 11 . 0 g ). ft - ir ( atr in cm − 1 ) 3332 ( uo — h ), 2946 ( uc — h ), 2883 ( uc — h ), 2089 ( un ≡ n ), 1258 ( uc — o ), 1045 ( uc — n ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 3 . 60 ( s , 1h , oh ), 3 . 47 ( t , 2h , 3 j = 6 . 4 hz , ch 2 oh ), 3 . 21 ( t , 2h , 3 j = 6 . 4 hz , ch 2 n 3 ), 1 . 61 ( qt , 2h , 3 j = 6 . 4 hz , 3 j = 6 . 4 hz , ch 2 c h 2 ch 2 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 58 . 63 ( ch 2 oh ), 47 . 74 ( ch 2 n 3 ), 30 . 94 ( ch 2 c h 2 ch 2 ) compound 66 ( 0 . 11 mol , 11 . 5 g ) is dissolved in dichloromethane ( 1 . 72 mol , 110 ml ). dmap ( 23 . 0 mmol , 2 . 78 g ) is added , followed by triethylamine ( 0 . 17 mol , 23 . 8 ml ). the reaction medium is placed at 0 ° c . a solution of tosyl chloride ( 0 . 17 mol , 32 . 41 g ) in dichloromethane ( 0 . 94 mol , 60 ml ) is added to the reaction . the reaction mixture is stirred for 15 hours while rising from 0 ° c . to room temperature . the reaction medium is diluted with 200 ml of dichloromethane and washed successively with 200 ml of saturated nahco 3 solution , 200 ml of 10 % by volume hcl solution and 200 ml of saturated nacl solution . the organic phase is dried over mgso 4 and the solvents are evaporated under reduced pressure . the residue is purified by conventional chromatography on silica gel with cyclohexane / et 2 o ( 80 : 20 to 60 : 40 ) elution gradient . compound 67 is obtained with a yield of 76 % ( 21 . 4 g ). ft - ir ( atr in cm − 1 ) 2957 ( uc — h ), 2095 ( un ≡ n ), 1598 ( uc ═ n ), 1356 ( uso 2 ), 1188 ( uso 2 ), 1172 ( uc — o ), 662 ( uso 2 ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 7 . 80 ( d , 2h , 3 j = 8 . 0 hz , ch ═ ch ), 7 . 38 ( d , 2h , 3 j = 8 . 0 hz , ch ═ ch ), 4 . 12 ( t , 2h , 3 j = 6 . 3 hz , ch 2 oso 2 ), 3 . 38 ( t , 2h , 3 j = 6 . 3 hz , ch 2 n 3 ), 2 . 45 ( s , 3h , ch 3 ), 1 . 89 ( q t , 2h , 3 j = 6 . 3 hz , ch 2 c h 2 ch 2 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 144 . 86 ( cso 3 ), 132 . 42 ( c ch 3 ), 129 . 73 ( ch ═ ch ), 127 . 54 ( ch ═ ch ), 67 . 01 ( ch 2 oso 2 ), 46 . 99 ( ch 2 n 3 ), 28 . 06 ( ch 2 c h 2 ch 2 ), 21 . 24 ( c ch 3 ) solanidine ( 0 . 25 mmol , 100 mg ) is placed under an inert atmosphere and dissolved in anhydrous thf ( 49 . 3 mmol , 4 ml ). ninety - five percent nah ( 0 . 50 mmol , 13 mg ) is then added and the reaction mixture is stirred at room temperature for 30 minutes . compound 67 ( 1 . 26 mmol , 0 . 32 g ) is then added and the solution is stirred at 60 ° c . for 24 hours . the solvents are evaporated under reduced pressure and then the residue is dissolved in chloroform and filtered through celite . after concentration of the filtrate , the residue obtained is purified by cpc ( conditions described above ). a mixture of solanidine and compound 75 is isolated . product 75 is recrystallized in acetonitrile with a yield of 71 % ( 85 mg ). hrms : 492 . 3919 ( 492 . 3930 calculated for c 30 h 51 n 3 ona ) ft - ir ( atr in cm − 1 ): 2991 ( u c — h ), 2216 ( u n ≡ n ), 1648 ( u c ═ n ), 1547 ( u c ═ c ), 1026 ( u c — o ) 1 h nmr ( cdcl 3 , 300 mhz ) δ 5 . 34 ( dd , 1h , 3 j 6 , 7a = 1 . 7 hz , 3 j 6 , 7b = 3 . 3 hz , h 6 ), 3 . 54 ( t , 2h , 3 j 3 ′″ 3 ″ = 6 . 2 hz , h 3 ′″ ), 3 . 39 ( t , 2h , 3 j 3 ′, 3 ″ = 6 . 7 hz , h 3 ′ ), 3 . 13 ( m , 1h , h 3 ), 2 . 35 ( ddd , 1h , 2 j 4a , 4b = 13 . 2 hz , 3 j 4a , 3 = 2 . 1 hz , j = 4 . 7 hz , h 4a ), 2 . 18 ( dd , 1h , 2 j 4b , 4a = 13 . 2 hz , 3 j 4b , 3 = 2 . 1 hz , h 4b ), 2 . 04 - 1 . 76 ( m , 4h ), 1 . 82 ( dt , 2h , 3 j 3 ″, 3 ′ = 6 . 7 hz , 3 j 3 ″, 3 ′″ = 6 . 2 hz , h 3 ″ ), 1 . 62 - 1 . 02 ( m , 22h ), 0 . 99 ( s , 3h , h 19 ), 0 . 91 ( d , 3h , 3 j 21 , 20 = 6 . 5 hz , h 21 ), 0 . 86 ( d , 3h , 3 j 27 , 25 = 6 . 6 hz , h 27 ), 0 . 85 ( d , 3h , 3 j 26 , 25 = 6 . 6 hz , h 26 ), 0 . 67 ( s , 3h , h 18 ) 13 c nmr ( cdcl 3 , 75 mhz ) δ 140 . 94 ( c 5 ), 121 . 73 ( c 6 ), 79 . 37 ( c 3 ), 64 . 54 ( c 3 ′ ), 56 . 89 ( c 14 ), 56 . 31 ( c 17 ), 50 . 32 ( c 9 ), 48 . 68 ( c 3 ′″ ), 42 . 44 ( c 13 ), 39 . 91 ( c 12 ), 39 . 64 ( c 24 ), 39 . 21 ( c 4 ), 37 . 35 ( c 1 ), 36 . 99 ( c 10 ), 36 . 33 ( c 22 ), 35 . 92 ( c 20 ), 32 . 06 ( c 7 ), 32 . 01 ( c 8 ), 29 . 73 ( c 3 ″ ), 28 . 50 ( c 2 ), 28 . 36 ( c 16 ), 28 . 12 ( c 25 ), 24 . 41 ( c 15 ), 23 . 98 ( c 23 ), 22 . 94 ( c 27 ), 22 . 69 ( c 26 ), 21 . 20 ( c 11 ), 19 . 48 ( c 19 ), 18 . 84 ( c 21 ), 11 . 97 ( c 18 ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 3 ( 0 . 10 mmol , 22 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 100 is obtained with a yield of 48 % ( 27 mg ). hrms : 699 . 4722 ( 699 . 4697 calculated for c 39 h 63 n 4 o 7 ) ft - ir ( atr in cm − 1 ): 3393 ( uo — h ), 2925 - 2854 -( uc — h ), 1076 - 1036 ( uc — o ) 1 h nmr ( pyridine - d 5 , 600 mhz ): 8 . 17 ( s , 1h , h glc1 ′″ ), 5 . 38 ( d , 1h , 2 j 1 ′ a , 1 ′ b = 12 . 3 hz , h glc1 ′ a ), 5 . 36 ( s , 1h , h 6 ), 5 . 17 ( d , 1h , 2 j 1 ′ b , 1 ′ a = 12 . 3 hz , h glc1 ′ b ), 5 . 07 ( d , 1h , 3 j 1 , 2 = 7 . 6 hz , h glc1 ), 4 . 57 ( dd , 1h , 2 j 6a , 6b = 12 . 0 hz , 3 j 6a , 5 = 2 . 4 hz , h glc6a ), 4 . 52 ( t , 2h , j = 9 . 8 hz , h 3 ′″ ), 4 . 38 ( dd , 1h , 2 j 6b , 6a = 12 . 0 hz , 3 j 6b , 5 = 5 . 3 hz , h glc6b ), 4 . 26 ( m , 2 h , h glc3 and h glc4 ), 4 . 09 ( m , 1h , h glc2 ), 3 . 98 ( m , 1h , h glc5 ), 3 . 60 ( s , 1h , h 26a ), 3 . 44 -( m , 3h , h 3 ′ and h 16 ), 3 . 08 ( m , 1h , h 3 ), 2 . 56 - 1 . 84 -( m , 6h , h 4 , h 3 ″ , h 22 and h 26b ), 1 . 72 - 1 . 10 ( m , 24h ), 0 . 93 ( s , 3h , h 19 ), 0 . 92 ( d , 3h , 3 j 21 , 20 = 13 . 1 hz , h 21 ), 0 . 91 ( m , 1h ), 0 . 75 ( d , 3h , 3 j 27 , 26 = 13 . 1 hz , h 27 ) 13 c nmr ( pyridine - d 5 , 150 mhz ): 145 . 63 ( c glc1 ″ ), 141 . 39 ( c 5 ), 124 . 71 ( c glc1 ′″ ), 121 . 68 ( c 6 ), 104 . 46 ( c glc1 ), 79 . 53 ( c 3 ), 78 . 95 ( c glc3 , c glc4 or c glc5 ), 78 . 89 ( c glc3 , c glc4 or c glc5 ), 75 . 87 ( c 22 ), 75 . 50 ( c glc2 ), 72 . 00 ( c glc3 , c glc4 or c glc5 ), 70 . 86 ( c 16 ), 64 . 56 ( c 3 ′ ), 63 . 48 ( c glc1 ′ ), 63 . 07 ( c glc6 ), 61 . 16 ( c 17 ), 59 . 08 ( c 26 ), 57 . 94 -( c 14 ), 50 . 44 -( c 9 ), 47 . 82 ( c 3 ′″ ), 40 . 91 ( c 13 ), 40 . 54 -( c 12 ), 39 . 76 ( c 4 ), 37 . 60 ( c 1 ), 37 . 50 ( c 10 ), 36 . 90 ( c 20 ), 32 . 54 -( c 24 ), 31 . 79 ( c 15 ), 31 . 56 ( c 3 ″ ), 31 . 40 ( c 25 ), 30 . 29 ( c 23 ), 29 . 04 -( c 8 ), 28 . 57 ( c 7 ), 27 . 35 ( c 2 ), 21 . 42 ( c 11 ), 19 . 66 ( c 19 ), 18 . 88 ( c 27 ), 16 . 87 ( c 18 ), 16 . 35 ( c 21 ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 6 ( 0 . 10 mmol , 22 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 101 is obtained with a yield of 55 % ( 31 mg ). hrms : 699 . 4711 ( 699 . 4697 calculated for c 39 h 63 n 4 o 7 ) ft - ir ( atr in cm − 1 ): 3378 ( uo — h ), 2934 - 2866 ( uc — h ), 1092 - 1041 ( uc — o ) 1 h nmr ( pyridine - d 5 , 600 mhz ): 8 . 11 ( s , 1h , h gal1 ′″ ), 5 . 42 ( d , j = 5 . 8 hz , 1h , h 6 ), 5 . 41 ( d , 1h , 2 j 1 ′ a , 1 ′ b = 12 . 3 hz , h gal1 ′ a ), 5 . 19 ( d , 1h , 2 j 1 ′ b , 1 ′ a = 12 . 3 hz , h gal1 ′ b ), 5 . 00 ( d , 1h , 3 j 1 , 2 = 7 . 7 hz , h gal1 ), 4 . 58 ( d , 1h , 3 j 4 , 3 = 3 . 0 hz , h gal4 ), 4 . 50 ( m , 5h , h 3 ′″ , h gal2 , h gal6a and h gal6b ), 4 . 19 ( dd , 1h , 3 j 3 , 4 = 3 . 0 hz , 3 j 3 , 2 = 9 . 4 hz , h gal3 ), 4 . 11 ( t , 1h , j = 5 . 9 hz , h gal5 ), 3 . 43 ( dq , 2h , j = 6 . 0 hz , j = 9 . 7 hz , h 3 ′ ), 3 . 17 ( dq , 1h , j = 11 . 3 hz , j = 6 . 6 hz , h 3 ), 2 . 93 ( dd , 1h , j = 10 . 3 hz , j = 2 . 5 hz , h 26a ), 2 . 67 ( m , 1h , h 16 ), 2 . 48 ( dd , 1h , j = 13 . 1 hz , j = 2 . 5 hz , h 4a ), 2 . 32 ( t , 1h , j = 11 . 3 hz , h 4b ), 2 . 12 ( q t , 2h , j = 6 . 6 hz , h 3 ″ ), 2 . 04 -( m , 1h ), 1 . 92 ( m , 1h ), 1 . 81 - 1 . 38 ( m , 18h ), 1 . 26 ( q , 1h , j = 13 . 0 hz , h 23b ), 1 . 14 -( m , 3h ), 1 . 03 - 0 . 93 ( m , 3h ), 0 . 99 ( s , 3h , h 19 ), 0 . 98 ( d , 3h , 3 j 21 , 20 = 5 . 9 hz , h 21 ), 0 . 96 ( s , 3h , h 18 ), 0 . 84 -( d , 3h , 3 j 27 , 26 = 6 . 4 hz , h 27 ), 0 . 82 ( m , 1h , h 24 ) 13 c nmr ( pyridine - d 5 , 150 mhz ): 145 . 78 ( c gal1 ″ ), 141 . 40 ( c 5 ), 124 . 19 ( c gal1 ″ ), 122 . 19 ( c 6 ), 105 . 06 ( c gal1 ), 79 . 64 -( c 3 ), 77 . 55 ( c gal5 ), 75 . 75 ( c gal3 ), 75 . 13 ( c 22 ), 72 . 90 ( c gal2 ), 70 . 67 ( c gal4 ), 69 . 62 ( c 16 ), 64 . 62 ( c 3 ′ ), 63 . 72 ( c 17 ), 63 . 40 ( c gal1 ′ ), 62 . 86 ( c gal6 ), 60 . 64 -( c 26 ), 58 . 14 -( c 14 ), 50 . 87 ( c 9 ), 47 . 85 ( c 3 ′″ ), 40 . 94 -( c 13 ), 40 . 45 ( c 12 ), 39 . 92 ( c 4 ), 37 . 76 ( c 1 ), 37 . 55 ( c 10 ), 37 . 28 ( c 20 ), 34 . 00 ( c 24 ), 32 . 77 ( c 8 ), 32 . 32 ( c 7 ), 31 . 90 ( c 15 ), 31 . 70 ( c 25 ), 31 . 64 -( c 3 ″ ), 29 . 97 ( c 23 ), 29 . 13 ( c 2 ), 21 . 63 ( c 11 ), 20 . 05 ( c 27 ), 19 . 87 ( c 19 ), 18 . 90 ( c 21 ), 17 . 39 ( c 18 ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 10 ( 0 . 10 mmol , 20 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 102 is obtained with a yield of 52 % ( 28 mg ). hrms : 683 . 4735 ( 683 . 4748 calculated for c 39 h 63 n 4 o 6 ) ft - ir ( atr in cm − 1 ): 3379 ( uo — h ), 2955 - 2854 -( uc — h ), 1076 - 1011 ( uc — o ) 1 h nmr ( pyridine - d 5 , 600 mhz ): 8 . 09 ( s , 1h , h rha1 ′″ ), 5 . 52 ( s , 1h , h rha1 ), 5 . 43 ( d , j = 2 . 8 hz , 1h , h 6 ), 5 . 19 ( d , 1h , 2 j 1 ′ a , 1 ′ b = 12 . 1 hz , h rha1 ′ a ), 4 . 97 ( d , 1h , 2 j 1 ′ b , 1 ′ a = 12 . 1 hz , h rha1 ′ b ), 4 . 57 ( m , 3h , h 3 ′″ and h rha2 ), 4 . 51 ( d , 1h , j = 6 . 5 hz , h rha3 or h rha4 ), 4 . 31 ( m , 2h , h rha5 and h rha3 or h rha4 ), 3 . 42 ( m , 2h , h 3 ′ ), 3 . 17 ( m , 1h , h 3 ), 2 . 96 ( d , 1h , j = 7 . 6 hz , h 26a ), 2 . 71 ( m , 1h , h 16 ), 2 . 49 ( d , 1h , j = 12 . 8 hz , h 4a ), 2 . 36 ( t , 1h , j = 11 . 8 hz , h 4b ), 2 . 16 ( m , 2h , h 3 ″ ), 2 . 04 -( d , 1h , j = 8 . 3 hz ), 1 . 94 -( d , 1h , j = 11 . 9 hz ), 1 . 81 - 1 . 27 ( m , 12h ), 1 . 14 -( m , 2h ), 0 . 99 ( m , 9h , h 18 , h 19 and h 21 ), 0 . 91 ( m , 4h ), 0 . 84 -( d , 3h , 3 j 27 , 26 = 10 . 8 hz , h 27 ) 13 c nmr ( pyridine - d 5 , 150 mhz ): 145 . 30 ( c rha ″ ), 141 . 41 ( c 5 ), 124 . 21 ( c rha1 ′″ ), 122 . 18 ( c 6 ), 101 . 39 ( c rha1 ), 79 . 67 ( c 3 ), 75 . 18 ( c 22 ), 74 . 35 ( c rha3 , c rha4 or c rha5 ), 73 . 13 ( c rha3 , c rha4 or c rha5 ), 72 . 59 ( c rha2 ), 70 . 47 ( c rha3 , c rha4 or c rha5 ), 69 . 68 ( c 16 ), 64 . 65 ( c 3 ′ ), 62 . 10 ( c 17 ), 61 . 07 ( c gal1 ′ ), 60 . 60 ( c 26 ), 58 . 15 ( c 14 ), 50 . 87 ( c 9 ), 47 . 94 -( c 3 ′″ ), 40 . 95 ( c 13 ), 40 . 47 ( c 12 ), 39 . 94 -( c 4 ), 37 . 76 ( c 1 ), 37 . 57 ( c 10 ), 37 . 28 ( c 20 ), 32 . 78 ( c 8 ), 32 . 30 ( c 7 ), 31 . 77 ( c 25 ), 31 . 65 ( c 3 ″ ), 31 . 15 ( c 15 or c 24 ), 30 . 74 -( c 15 or c 24 ), 30 . 37 ( c 23 ), 29 . 13 ( c 2 ), 21 . 63 ( c 11 ), 20 . 02 ( c 27 ), 19 . 95 ( c rha6 ), 19 . 87 ( c 19 ), 19 . 03 ( c 21 ), 17 . 39 ( c 18 ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 19 ( 0 . 10 mmol , 22 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 103 is obtained with a yield of 63 % ( purity not confirmed by nmr ). empirical formula : c 39 h 62 n 4 o 5 s hrms : 699 . 4515 ( 699 . 4519 calculated for c 39 h 63 n 4 o 5 s ) ft - ir ( atr in cm − 1 ): 3383 ( uo — h ), 2926 ( uc — h ), 1122 - 1010 ( uc — o ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 28 ( 0 . 10 mmol , 38 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 104 is obtained with a yield of 59 % ( purity not confirmed by nmr ). empirical formula : c 45 h 72 n 4 o 10 s hrms : 861 . 5039 ( 861 . 5047 calculated for c 45 h 73 n 4 o 10 s ) ft - ir ( atr in cm − 1 ): 3339 ( uo — h ), 2935 - 2877 ( uc — h ), 1056 ( uc — o ) compound 75 ( 0 . 08 mmol , 40 mg ) and compound 56 ( 0 . 10 mmol , 51 mg ) are dissolved in 3 . 75 ml of a mixture of 1 , 4 - dioxane and h 2 o ( 4 : 1 by volume ). copper ( ii ) sulfate ( 0 . 12 mmol , 19 mg ) and sodium ascorbate ( 0 . 23 mmol , 47 mg ) are then added . the reaction medium is stirred at 80 ° c . for 24 hours . the mixture is filtered through celite and the collected filtrate is concentrated under reduced pressure . the residue is purified by cpc . compound 105 is obtained with a yield of 67 % ( purity not confirmed by nmr ). hrms : 991 . 5820 ( 991 . 5855 calculated for c 51 h 83 n 4 o 15 ) ft - ir ( atr in cm − 1 ): 3347 ( uo — h ), 2931 ( uc — h ), 1126 - 980 ( uc — o ) the macrosiphum euphorbiae population was initiated from an apterous female provided by the laboratory of functional biology , insects and interactions of the inra / insa of villeurbanne in 2004 . she was captured in 1995 on an eggplant in the rhone - alps region . the macrosiphum euphorbiae aphids were raised on desiree variety potato plants indoors at 20 ± 1 ° c ., 60 ± 5 % relative humidity and under a photoperiod of 16 hours of light and 8 hours of darkness . for the tests on macrosiphum euphorbiae larvae , adults were isolated and placed in pvc cages on artificial medium for one day in order to synchronize their lineage . neonates ( 40 per experiment ), less than 24 hours old , are placed in pvc cages containing artificial medium alone ( control experiment ) or artificial medium supplemented with 0 . 002 , 0 . 02 or 0 . 2 mm active compound . for the tests on macrosiphum euphorbiae adults , neonates ( 50 per experiment ) resulting from synchronization are raised in petri dishes on leaves of desiree variety potato plants for 10 days . once the adult stage is reached , they are placed in pvc cages containing artificial medium alone ( control experiment ) or artificial medium supplemented with 0 . 002 , 0 . 02 or 0 . 2 mm active compound . the individuals were monitored every two days over a period of 16 days . with each recording , the artificial medium is changed . each cage houses five aphids . a standard diet was used as the basis for carrying out the physiological monitoring . its composition was described by febvay et al . ( j . zool . 1988 , 66 ( 11 ), 2449 - 2453 ) and then modified according to the conditions of down et al . ( j . insect physiol . 1996 , 42 ( 11 - 12 ), 1035 - 1045 ) as shown in table 2 . the medium is supplemented with active compound and placed between two layers of parafilm ® in sterile conditions . the statistical analyses were performed using the statistica 10 software ( statsoft ®). to compare aphid survival in comparison with the control , pearson &# 39 ; s x 2 test ( α & lt ; 0 . 05 ) was applied . to compare the compounds in terms of concentration and nature , fisher &# 39 ; s least significant difference ( lsd ) test was applied ( α & lt ; 0 . 05 ). daily fecundity was also studied using fisher &# 39 ; s lsd test ( α & lt ; 0 . 05 ). the biological tests were carried out on macrosiphum euphorbiae neonates less than 24 hours old . they are placed on artificial medium containing chaconine , solanine , solanidine , 100 , 101 or 102 . fig2 a and 2b show the variation in mortality over time . fig1 a shows the effects on larval survival of compounds 100 , 101 and 102 according to the invention . the results were analyzed using pearson &# 39 ; s x 2 test , wherein α = 0 . 05 , * indicates that there is a significant difference in comparison with the control . fig1 b shows the effects on larval survival of chaconine , solanine and solanidine . the results were analyzed using pearson &# 39 ; s x 2 test , wherein α = 0 . 05 , * indicates that there is a significant difference in comparison with the control . according to these results , the aphicide activity of the synthetic glycoalkaloids is marked in comparison with the control . moreover , the same is true with respect to 0 . 2 mm solanidine , which shows the best result among the natural molecules . generally , 0 . 002 mm synthetic glycoalkaloids have lower activity than 0 . 2 mm solanidine ( p & lt ; 0 . 001 for compounds 100 and 102 and p = 0 . 006 for compound 101 ). if the concentrations of 100 , 101 and 102 are increased to 0 . 02 mm , the survival rates are 26 %, 33 % and 32 %, respectively . at this concentration , the aphicide properties with respect to larvae become stronger than with solanidine . this observation is even more marked for the 0 . 2 mm concentrations , where larval survival is 22 %, 24 % and 6 % for 100 , 101 and 102 , respectively ( p & lt ; 0 . 001 ). the results of this test after 16 days of treatment are presented in table 3 below . the values are expressed as a percentage . obviously , the lower the value , the more powerful the compounds . as table 3 shows , the compounds according to the invention have very low values compared with the natural glycoalkaloids . consequently , the very powerful aphicide effects of the compounds according to the invention compared with natural glycoalkaloids were shown . compound 100 has no significant activity in comparison with the control at concentrations of 0 . 002 mm and 0 . 02 mm . however , a notable effect is observed at 0 . 2 mm ( p & lt ; 0 . 001 ) with a mortality rate of 54 %. concerning compound 101 , an increase in the concentration to 0 . 02 and 0 . 2 mm makes it possible to observe a drop in the survival rate of macrosiphum euphorbiae adults ( p = 0 . 006 and p & lt ; 0 . 001 , respectively ). lastly , compound 102 has no significant aphicide activity at the lowest concentration , but , just like compound 101 , an increase in the concentration of the compound to 0 . 02 and 0 . 2 mm makes it possible to observe a marked effect on the survival of adults ( p & lt ; 0 . 001 for both experiments ). the results of this test after 16 days of treatment are presented in table 4 below . the values are expressed as a percentage . as table 4 shows , the compounds according to the invention have very low values in comparison with the control . data regarding the number of larvae resulting from parthenogenesis can be used to calculate daily fecundity per aphid . the results are presented in fig3 , wherein the number 10 represents the control , the reference numbers 12 , 14 and 16 represent the results of compound 100 at the concentrations of 0 . 002 , 0 . 02 and 0 . 2 mm , respectively , the reference numbers 18 , 20 and 22 represent the results of compound 101 at the concentrations of 0 . 002 , 0 . 02 and 0 . 2 mm , respectively , the reference numbers 24 , 26 , and 28 represent the results of compound 102 at the concentrations of 0 . 002 , 0 . 02 and 0 . 2 mm , respectively . as for survival rate , the presence in the artificial medium of the compounds according to the invention can have an impact on reproduction . in comparison with the control experiment , compounds 100 , 101 and 102 at concentrations of 0 . 02 and 0 . 2 mm significantly reduce reproduction ( p & lt ; 0 . 001 ). as described in detail above , the compounds according to the invention have the following advantages : the structural changes provided by the synthesis make it possible to increase the toxicity of glycoalkaloids , in particular on macrosiphum euphorbiae larvae or adults . the compounds according to the invention could be used as insecticides against other potato - infesting species but also against insects not specific to this plant . unlike natural glycoalkaloids , in which a trisaccharide is essential , a single saccharide unit would be sufficient to generate aphicide activity with the compounds according to the invention . the compounds according to the invention have a structure that is relatively simple and easy to synthesize . the compounds according to the invention have insecticidal properties ( insect behavior is not affected , but the compound acts on demographic parameters like survival and reproduction ).— the compounds according to the invention can be obtained from chaconine and from solanine , themselves obtained from coproducts of the potato industry , which makes it possible to exploit them . lastly , the compounds according to the invention have other possible activities , such as bactericidal , fungicidal , nematicidal , antiviral or antitumoral properties .
novel solanidine - derived compounds , the synthesis method thereof and the uses of same in the fields of phytosanitary protection and health . in particular , the novel compounds have toxic and / or repellent properties in relation to aphids , as well as other properties .