, IR (neat) (?, cm -1 ) = 1747 (C=O), 1431, MS (ESI + ) m/z ([M+H] + ): 348. brine, dried over anhydrous MgSO 4 , filtered and the solvent removed, p.1203, 1371.
, CDCl 3 ) ? (ppm) = 7.59 (d, 1H13 (d, 0.3H, 3 J(1-2) = 6.5 Hz, H 1z ), 5.1 (dd, 0.3H, 3 J(2-1) = 6, ) = 7.9 Hz, H 1E ) (d, 1H, 2 J = 11.4 Hz, CH 2 Bn E ) Hz, CH 2 Bn Z ), 4.47 (d, 1H, 2 J = 11.7 Hz, CH 2 Bn E ), pp.3-4, 1977.
, Data for the E isomer (only traces of the Z isomer could be detected by 13 C NMR)
, 40); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7.96 (s, 0.25 H, OH Z ), 7.67 (s, 1H, ) = 7.7 Hz, H 1E ), pp.6047-6048
, 13 C NMR (100 MHz, CDCl 3 )?? (ppm) = 150.7 (C-1 E ), Cq Ar)
, CDCl 3 ) ? (ppm) = 170, CDCl 3 ) ? (ppm) = 7.72 (d, 1H, 3 J(1-2) = 7.8 Hz 1H, 2 J = 11.7 Hz, CH 2 Bn), 4.59 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), 4.48 (d, 1H, 2 J = 11.7 Hz, CH 2 Bn), 4.44 (dd, 1H, 3 J(2-1) = 7.8 Hz, 3 J(2-3) = 5.1 Hz (m, 1H, H 4 ), 3.76 (t, 3 J(3-2) = 3 J(3-4) = 4.9 Hz, H 3 )CH 2 Bn), 72.0 (CH 2 Bn), pp.42-49, 1990.
, 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7.60 (s, 0, 8H, OH E ), 7.47 (d, 1H, 3 J(1-2) = 7.8 Hz H, H 2Z ), 4.72 (d, 1H, 2 J = 11.6 Hz, CH 2 Bn E ), 4.68-4.59 (m, 5H, CH 2 Bn E+Z ), pp.37-44
, CDCl 3 ) ? (ppm) = 170, C=O E )
, CH 3 Ac); IR (neat) (?, cm -1 ) =, 63.6 (C-5 E ), pp.3030-1738, 1088.
, Purification by silica gel column chromatography (PE/EtOAc : 70/30) gave the product 234 as a mixture of E/Z isomers in a 85/15 ratio (19.1 g, 81%) as a pale yellow oil. Data for the E isomer (only traces of the Z isomer could be detected by 1 H NMR): R f = 0.57 (PE/ EtOAc: 70/30); [ ] = + 27.1 (c = 0.92 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, General procedure 2 was followed30-5.20 (m, 1H, H 5 ), 4.67 (d, 1H, ²J = 11.6 Hz, CH 2 Bn Hz, CH 2 Bn), 4.53 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), pp.52-56
, 00 (s, 3H, CH 3 Ac); 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 170, Cq Ar), 128.7 (CH Ar, p.8080679
, EtOAc : 70/30); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7.50 (d, 1H, ) = 7.7 Hz, H 1E ), pp.3-4
, CDCl 3 )?? (ppm) (only shifts for the main E isomer could be detected) = 170, C NMR (62.5 MHzCq Ar), 137.6 (Cq Ar), 128.54 (CH Ar), 128.51 (CH Ar)CH Ar), 127.75 (CH Ar), 127.72 (CH Ar)CH 2 Bn), 74.5 (CH 2 Bn), 73.2 (CH 2 Bn)CH 3 Ac); IR (neat) (?, pp.1-98
, CH 3 SEt); IR (neat) (?, cm -1 ) =, CH Ar, vol.61, issue.912, pp.3029-1043, 1066.
, of sodium methoxide (3 mg of Na in MeOH (0.5 mL), 0.15 mmol) for 12h. Purification by silica gel column chromatography (PE/EtOAc : 70/30) gave the desired compound 232 as a colourless oil
, J(6b-6a) = 9.7 Hz, 3 J(6b-5) = 3.8 Hz, H 6b ), 3.19 (q, 2H, 3 J = 7.3 Hz, CH 2 S), 1.23 (t, 3H, 3 J = 7.3 Hz, CH 3 SEt ); 13 C NMR (62.5 MHz, acetone-d 6 )?? (ppm) = 151, Cq Ar), vol.35, issue.1292, p.72
, 95/5), the desired compound 263 as a colourless oil (347 mg, 50% over two steps) along with the desilylated compound (126 mg, p.20
, ); 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) =
, 0.19 (s, 3H
, NMR (62.5 MHz CDCl 3 ) ?? (ppm) = 155
, EtOAc); m.p. 91.1-91.5°C; [ ] = + 5.0 (c = 0.96 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7, 4.70 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn), 4.63 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn), 4.62 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn), 4.58 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn), pp.4-55, 2361.
, After stirring at reflux until TLC showed complete consumption of the starting material, silica was added to the reaction mixture, the solvent was evaporated under pressure and the compound was purified by silica gel column chromatography
, 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7, 4.86 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), 4.76 (d, 1H, 2 J = 11.7 Hz, CH 2 Bn), 4.75 (d, 1H, 2 J = 11.4 Hz, CH 2 Bn (d, 1H, 2 J = 10.6 Hz, CH 2 Bn), 4.49 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn Bn), 4.22 (d, 1H, 2 J = 11.1 Hz, CH 2 Bn)) = 9.3 Hz, pp.38-45, 1960.
, CH 3 SEt); IR (neat) (?, cm -1 ) = 3029 (C sp2 -H Ar, 1H, CH 2 S), 2.83 (dq, 1H, 2 J = 12.2 Hz, 3 J = 7.4 Hz, CH 2 S), 1.21 (t, 3H, 3 J = 7.4 Hz, pp.109027-109030, 1208.
, 78 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, 4.96 (d, 1H, 2 J = 11.7 Hz, CH 2 Bn), 4.84 (d, 1H, 2 J = 11.2 Hz, CH 2 Bn CH 2 Bn), 4.72 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.70 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn 4.54 (d, 1H, 2 J = 11.3 Hz, CH 2 Bn)) = 10.2 Hz, pp.38-45
, CH 3 SEt ); 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 143, 3H, 3 J = 7.4 Hz, pp.85-87
, CH 3 SEt); IR (neat) (?, cm -1 ) = 3029 (C sp2 -H Ar), CH Ar, vol.717, issue.694, pp.1210-794, 1307.
, 59 (d, 3 J(1-2) = 8, pp.40-47
, 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 149, 3.74 (dd, 1H, 2 J(6b-6a) = 11.2 Hz, 3 J(6b-5) = 7.4 Hz, H 6b ), 2.90 (s, 3H, CH 3 Ms ) 128.02 (CH Ar), 127.98 (CH Ar), 127.96 (CH Ar), 127.92 (CH Ar), 127.88 (CH Ar) 79.7 (C-4 or C-3) 1H, H 5 ), 4.93 (d, 1H, 2 J = 10.9 Hz, CH 2 Bn), 4.73 ? 4.55 (m, 5H, CH 2 Bn Bn), 4.15 (dd, 1H, 3 J(3-2) = 7.7 Hz, 3 J(3-4) = 5.9 Hz CH 3 SEt ); 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 152.1 (C-1), pp.7368615852473025-4
, 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7.75 (d, 2H, 3 J = 8, 2H, 3 J = 8.1 Hz, H Ar ), 7.09 (dd, 2H, 3 J = 6.4 Hz, 3 J = 3.0 Hz 2H, CH 2 Bn), 4.66 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.44 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn 1H, H 5a ), 4.24 (dd, 1H, 2 J(5a-5b) = 13 C NMR (100 MHz, CDCl 3 ) ? (ppm) = 140.8 (Cq Ar), pp.43-50
, Me); IR (neat) ? (cm -1 ) = 3030, CH Ar, vol.72, issue.852, pp.2917-1517, 1070.
, 4 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, 4H, CH 2 Bn), 4.43 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), 4.36 (d, 1H C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 160, pp.88-95
, IR (neat) ? (cm -1 ) = 2932, OMe)CH Ar, vol.72, issue.831, pp.1509-745, 1070.
, 6 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, pp.50-57
, 7 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 8, J = 11.9 Hz, CH 2 Bn Hz, CH 2 Bn), 4.42 ? 4.35 (m, 1H, H 5a ), pp.21-29
, H 3 ); 13 C NMR (100 MHz, CDCl 3 ) ? (ppm) = 147, pp.4-12
, 9 (c = 1.0 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 8.51 (t, 1H, 3 J = 1.9 Hz, H Ar ) 2H, H Ar ), 4.73 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn) 4.49 (d, 1H, 2 J = 11.6 Hz, CH 2 Bn), 4.39 (d, 1H, 2 J = 11.6 Hz, CH 2 Bn), 4.36 (dd, 1H, pp.21-29
, H 4 ); 13 C NMR (100 MHz, CDCl 3 ) ? (ppm) = 148, Cq Ar)CH Ar), 133.7 (Cq Ar), pp.4-26
, 09 (dd, 1H, 3 J(1'-2'trans) = 18.1 Hz, 3 J(1'-2'cis) = 11.7 Hz, H 1' ), 5.83 (d, 1H, 3 J(2'trans-1') = 18.1 Hz, H 2'trans ), 5.55 (d, 1H, 3 J(2'cis-1') = 11, J = 11.9 Hz, CH 2 Bn), pp.40-47, 2002.
, 6 (c = 1.2 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, 3H, CH 2 Bn), 4.68 ? 4.62 (m, 1H, H 2 ), pp.64-71
, CDCl 3 ) ? (ppm) = 142, C NMR (62.5 MHzCq Ar), pp.128-149
, C-6); IR (neat) ? (cm -1 ) = 3030, 74.3 (CH 2 Bn), 74.0 (CH 2 Bn), 73.5 (CH 2 Bn), 73.1 (CH 2 Bn) 1496, 1452, 1277, 1205, pp.74-81
, CDCl 3 ) ? (ppm) = 7, CHCl 3 ); 1 H NMR (250 MHz 4.89 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), 4.80 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn), 4.85 ? 4.76 (m, 1H, H 2 ), 4.78 6b ), 4.18 (d, 1H, 2 J = 11.0 Hz, CH 2 Bn) C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 144, pp.73-80, 2003.
, 2 (c = 1.3 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7, J = 11.2 Hz, CH 2 Bn), 4.80 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn), 4.74 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn) 4.67 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.66 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.62 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.57 (d, 1H, pp.71-78
, 21 mmol, 1 equiv.), phenylboronic acid (56 mg, 0.46 mmol, 2.2 equiv.), CuMeSal (99 mg, 0.46 mmol, 2.2 equiv.) were added in a dried microwave vial. Degased THF (1 mL) was introduced and then, Pd(PPh 3 ) 4 (5 mol%) was added. After stirring for 12h at reflux, the resulting crude mixture was evaporated with silica, purified by silica gel chromatography, p.72
, (c = 1.3 in CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 8, 5.15 (bs, 1H, H 3 ) Hz, CH 2 Bn), 4.68 (d, 1H, 2 J = 11.5 Hz, CH 2 Bn, pp.20-28
, 11 mmol, 1 equiv.), phenylboronic acid (30 mg, 0.23 mmol, 2.2 equiv.) and CuMeSal (50 mg, 0.23 mmol, 2.2 equiv
, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) ? (ppm) = 7, 6.83 (d, 1H, 3 J = 7.7 Hz, H Ar ), 5.15 (d, 1H, 2 J = 11.4 Hz, CH 2 Bn J = 11.6 Hz, CH 2 Bn), 4.67 (d, 1H, 2 J = 11.4 Hz, CH 2 Bn)) = 6.5 Hz) = 4.2 Hz, H 5a ), 3.69 (dd, 1H) = 11.6 Hz) = 6.4 Hz, H 5b ), pp.45-52, 2002.
, ); IR (neat) ? (cm -1 ) = 3063, 128.59 (CH Ar), 128.5 (CH Ar), 128.12 (CH Ar), 128.06 (CH Ar) 74.6 (CH 2 Bn) HRMS (ESI + ): m/z calculated for C 32, pp.6362-2863, 1101.
, 50); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, (d, 1H, 2 J = 11.2 Hz, CH 2 Bn, CH 2 Bn), 4.73-4.61 (m, 2H, CH 2 Bn), 4.56 (d, 1H, 2 J = 12.1 Hz, CH 2 Bn), 4.48 (d, 1H, pp.5038-5045, 1989.
, CD 3 OD) ? (ppm) = 155, C NMR (62.5 MHzCH 3 SEt); IR (neat) (?, pp.1074-238, 1257.
, IR (neat) ? (cm -1 ) = 3256, 73.9 (C-4), 73.3 (CH 2 Bn), 72.7 (CH 2 Bn) 52.7 (C-2' or COOMe), 52.3 (C-2' or COOMe), 31.7 (CH 2 S), pp.7369-128, 1073.
, N-allyl-2,3,4-tri-O-benzyl-5-(hydroxyimino)pentanamide 415
, HRMS (ESI + ): m/z calculated for C 34 H 45, CH Ar, pp.695-545
, 3 (c = 1.2 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, pp.43-50
, H 5a , H 5b , H 1'a , H 1'b ) 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) = 145, Cq Ar), vol.40139, issue.1285, pp.4-46
, (C-1'); IR (neat) ? (cm -1 ) = 3030, 75.5 (C-3), 73.2 (CH 2 Bn)CH 2 Bn), 70.7 (CH 2 Bn), pp.2860-1029, 1077.
, 1 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, 1H, NH), 4.79 (d, 1H, 2 J = 11.7 Hz, CH 2 Bn), 4.66 (d, 1H, 2 J = 11.8 Hz, CH 2 Bn) Bn), 4.46 (d, 1H, 2 J(2-3) = 3.7 Hz (t, 1H, 3 J = 7.3 Hz, H 3' ). 13 C NMR (62.5 MHz, CDCl 3 ) ? (ppm) =, pp.38-45
, 0 in CHCl 3 ); 1 H NMR (250 MHz, CDCl 3 ) ? (ppm) = 7, 6.91 (bs, 1H, NH), 4.69 (d, 1H, 2 J = 11.6 Hz, CH 2 Bn), 4.66 (d, 1H CH 2 Bn), 4.53 (d, 1H, 2 J = 11.9 Hz, CH 2 Bn), 4.55 ? 4.51 (m, 1H, CH 2 Bn)) = 10.2 Hz, 3 J(6a-5) = 6.9 Hz, H 6a ), pp.37-44
, une enzyme clé dans la formation des glucosinolates Les travaux menés ont tout d'abord été axés sur la synthèse d'acides thiohydroxamiques, substrats de la S-UGT, pour l'étude cinétique de l'enzyme. Dans ce but, nous avons envisagé différentes méthodes et avons pu obtenir les molécules ciblées
, This thesis is articulating into three topics: (1) synthesis of thiohydroxamic acids) the synthesis and (3) the study of the reactivity of thioimidate N-oxides (TINOs) The purpose of these works is the study of the enzyme: S-glycosyltransferase