反応 #577238

反応方程式

5

1,1′-[(Pentane-1,5-diyl)dioxy]-bis[(11S,11aS,2Z)-10-(allyloxycarbonyl)-11-hydroxy-7-methoxy-2-ethylidene-1,2,3,10,11,11a-hexahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one]

triphenylphosphine

pyrrolidine

CHCl3 MeOH

→

1

1,1′-[(Pentane-1,5-diyl)dioxy]-bis[(11aS,2Z)-7-methoxy-2-ethylidene-1,2,3,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one]

溶媒

CH2Cl2

反応条件

後処理

1. 1
   その他the progress of reaction
2. 2
   workup.WAITAfter two and a half hours TLC revealed
3. 3
   その他to give a spot which
4. 4
   その他The solvent was evaporated under reduced pressure

実験手順

A catalytic amount of tetrakis(triphenylphosphine)palladium (14.4 mg, 12.5 μmol) was added to a stirred solution of the bis-alloc-carbinolamine 5 (200 mg, 0.25 mmol), triphenylphosphine (6.30 mg, 24.1 μmol) and pyrrolidine (33 mg, 40.1 μL 0.48 mmol) in CH2Cl2 (13 mL) under a nitrogen atmosphere. The reaction mixture was allowed to warm to room temperature and the progress of reaction monitored by TLC (95:5 v/v CHCl3/MeOH). After two and a half hours TLC revealed the reaction was complete to give a spot which fluoresced brightly under UV light. The solvent was evaporated under reduced pressure and the resulting residue subjected to flash chromatography (98:2 v/v CHCl3/MeOH) to give the bis-imine target molecule 1 as a pale orange glass which was repeatedly evaporated in vacuo with CHCl3 to provide the imine form. Yield=160 mg (Quant); [α]21D=+937° (c=0.641, CHCl3); 1H NMR (250 MHz, CDCl3) δ 7.67 (d, 2H, J=4.5 Hz), 7.50 (s, 2H) 6.80 (s, 2H), 5.63-5.55 (m, 2H), 4.38-3.96 (m, 8H), 3.94 (s, 6H), 3.86-3.80 (m, 2H), 3.20-3.03 (m, 2H), 2.90 (d, 2H, J=15.8 Hz), 2.00-1.91 (m, 4H), 1.76-1.68 (m, 8H); 13C NMR (62.9 MHz, CDCl3) δ 164.9, 163.0, 150.8, 147.8, 140.6, 132.9, 119.8, 119.3, 111.4, 110.3, 68.7, 56.1, 53.4, 48.3, 35.3, 28.6, 22.5, 14.9; MS (FAB) m/z (relative intensity) 613 ([M+H]+, 52), 443 (26), 421 (22), 329 (100), 307 (71), 242 (35), 220 (38); IR (CHCl3) 3220 (br), 2940, 2859, 1697, 1602, 1560, 1508, 1458, 1432, 1382, 1341, 1263, 1217, 1132, 1098, 1065, 1007, 875, 666 cm−1; HRMS [M+H]+ calcd for C35H41N4O6 m/z 613.3026, found (FAB) m/z 613.3047.

出典