Studies on the syntheses of spiro-dienone compounds. VI. A new synthesis of dl-pronuciferine.

Aporphine Glycosides from Stephania cepharantha Seeds

“…The n-hexane extract was repeatedly subjected to a combination of column chromatography, preparative TLC, and crystallization, to afford 10 known aporphine alkaloids: dehydrostephanine (3), 4 dehydrocrebanine (4), 6 stephanine (5), 7 crebanine (6), 7 (-)-dicentrine (7), 8 (-)-roemerine (8), 9 (-)-isolaureline (9), 10 nuciferine (10), 11 stesakine (11), 6 and N-methylasimilobine (12). 11 The MeOH extract was fractionated, and the alkaloid-containing fraction was purified using the same methods as for the fractionation of the n-hexane extract, to give stesakine-9-O-β-D-glucopyranoside (1) and N-methylasimilobine-2-Oβ-D-glucopyranoside (2), as well as nine known alkaloids: four aporphines, 6, 11, 12, and (-)-cassythicine (13); 12 one proaporphine, pronuciferine (14); 13 and four bisbenzylisoquinolines, cepharanthine, 14 cepharanoline, 15 isotetrandrine, 16 and berbamine. 17 Glycoside 1 was obtained as an amorphous powder.…”

“…The first fraction (55 mg) was separated by preparative TLC to yield 6 (8 mg), 11 (18 mg), cepharanthine (4 mg), and isotetrandrine (5 mg) . The 51-mg fraction was also purified by preparative TLC to afford 12 (18 mg), (−)-cassythicine ( 13 , 4 mg), pronuciferine ( 14 , 2 mg), cepharanoline (3 mg), and berbamine (12 mg) . The final fraction (38 mg) was separated by preparative TLC [with EtOAc−MeOH (1:2)] to afford stesakine-9- O -β- d -glucopyranoside ( 1 , 5 mg) and N -methylasimilobine-2- O -β- d -glucopyranoside ( 2 , 10 mg).…”

“…IR spectra were obtained on an FT/IR-5000 (JASCO) spectrometer using KBr disks. NMR spectra were recorded on a JNM-R500 (JEOL) (500 MHz for 1 H and 125 MHz for 13 C) spectrometer with tetramethylsilane as internal standard. MS were recorded on a JMS-HX110A (JEOL) spectrometer for EIMS and FABMS, and a JMS-D300 (JEOL) spectrometer was used for HRMS.…”

“…6 Hz, H-11), 5.98 (d, J ) 1.2 Hz, OCH 2O), 6.11 (d, J ) 1.2 Hz, OCH2O), 2.48 (s, N-CH3), 4.01 (s, 8-OCH3), 5.71 (d, J ) 7. 3 Hz, H-1′), 4.38 (m, H-2′), 4.38 (m, H-3′), 4.35 (m, H-4′), 4.19 (ddd, J ) 8.9, 5.5, 2.1 Hz, H-5′), 4.42 (dd, J ) 11.9, 5.5 Hz, H-6′), 4.60 (dd, J ) 11.9, 2.1 Hz, H-6′); 13 C NMR (pyridine-d5, 125 MHz) δ 142.7 (s, C-1), 147.12 (s, C-2), 107.4 (d, C-3), 127.32 (s, C-3a), 29.6 (t, C-4), 53.9 (t, C-5), 62.47 (d, C-6a), 27.5 (t, C-7), 130. (8), 325 (64), 324 (100), 308 (19), 282 (34), 280 (10), 267 (6), 264 (7), 251 (7) H NMR (pyridine-d5, 500 MHz) δ 7.39 (s, H-3), 2.50 (dd, J ) 17.7, 3.4 Hz, H-4), 3.11 (ddd, J ) 17.7, 11.9, 5.5 Hz, H-4), 2.23 (ddd, J ) 11.9, 11.6, 3.4 Hz, H-5), 2.84 (dd, J ) 11.6, 5.5 Hz, H-5), 2.96 (dd, J ) 13.7, 4.0 Hz, H-6a), 2.75 (dd, J ) 13.7, 13.7 Hz, H-7), 3.21 (dd, J ) 13.7, 4.0 Hz, H-7), 7.38 (d, J ) 7.…”

Total syntheses of natural products containing spirocarbocycles

“…Photolysis has been used by the Iwata and Fukumoto groups. to synthesise pronuciferine, 191,192 orientalinone, 193 O-methyl-orientalinone, 194 and O-methyl-kreysiginone 195 (Scheme 62).…”