W0 2011/000721 A1 I||||||||||||||||||||||||||||||||||||||||||||||||||||||||| - Questel

To a solution of the compound 9 (124.5 mg, 0.1066 mmol, 1 eq) in dry MeOH
(2.13 ml_) under nitrogen atmosphere 213 μl_ of MeONa 1M were added. The
reaction was stirred at room temperature monitoring by TLC (8:2
CH 2 C I 2 :Et0Ac, 75:25:3 CHCI 3 :MeOH:H 2 O). After 20 minutes the reaction was
finished and the solution was neutralized with Amberlite IRA 120H + , the resin
removed by filtration and the solvent was evaporated at reduced pressure,
obtaining pure 2b as a colourless oil (70.1 mg, quantitative).
[af° = + 59.38 (c: 1.025, CH 3 OH). 1 H-NMR (400 MHz, CD 3 OD) δ (ppm): 4.94
(d, 1H, H 1M Ji- 2 = 1 Hz), 4.82 (d, 1H, H , J r . 2 . = 1.2 Hz), 4.07 (bs, 1H, D 2 ),
3.96-3-92 (m, 1H, H 7 ), 3.88-3.81 (m, 4H, H 2M , H 2M ., H 66 M , H 6B M), 3.78-3.74 (m,
2H, D 1 , H 6AM '), 3.74-3.67 (m, 4H, H 6A M , H 7A , H 3M , H 3M -), 3.65 (s, 3H, OCH 3 ),
3.65 (S, 3H, OCH 3 ), 3.66-3.61 (m, 4H, H 4 M H 5 M-, H 5 M, H 4M ), 3.43 (t, 2H, H 8 , J 7 8
= 4.8 Hz), 3.00 (dt, 1H, D 5 , =12.8 Hz, 3.6 Hz), 2.84 (dt,
1H , D 4 , J D 4 -D 3
= 11.6 Hz, J D4 . D3 βq= 3.6 Hz), 2.16 (app d , 1H, D 6ax , J gem = 13.6
Hz), 2.04 (app d , 1H, D 3ax , J gem = 14.0 Hz), 1.84 (t, 1H, D 3θq ), 1.74 (t, 1H, D 6θq ).
13 C-NMR ( 100 MHz, CD3 OD) δ (ppm): 177.25, 176.99 (COOCH 3 ), 101 .87
(C1 MO. 100.35 (C1 M ), 76.06 (C1 D ), 75.49 (C4 M ), 74.24 (C4 M ), 72.59, 72.58,
72.53 (C2 M , C2 M ., C 3 M , C 3 M ), 7 1.94 (C2 D ) , 70.00 (C6 M ), 68.59 (C5 M , C5 M ),
63.03 (C6 M ), 52.33 (OCH 3 ), 5 1.76 (C 8 ), 40.39 (C4 D ), 40.13 (C5 D ), 28.92 (C6 D ),