Narcissus and Daffodil

More documents

Recommendations

Info

MeO MeN HO O HO (–)-1 OH O NMe OMe NR 5 (R=H) 6 (R=Me) OH MeO MeO MeN OR O HO O O Synthesis of galanthamine 305 equilibrium process as shown in Figure 12.1. Enantiomeric (–)-2, on reduction with different agents, produces a mixture of (–)-1 and (–)-epi-galanthamine ((–)-4). The key compound in the biosynthesis of (–)-1 and related Amaryllidaceae alkaloids is norbelladine (5, R = H; Figure 12.1), which is formed from tyrosine (Barton and Cohen, 1957; Barton et al., 1961, 1962, 1963; Schutte, 1969). O 3 O NMe NMe OMe MeO MeN O HO OH (–)-2 (–)-4 (+)-1 (+)-2 (+)-4 Figure 12.1 (Above) The equilibrium process between narwedine hydrohydienone (3) and its enantiomers (2) and oxidative/reductive interconversion between (2) and galanthamine (1) and epi-galanthamine (4) enantiomers. (Below) Norbelladine (5) and N,O-dimethylnorbelladine (6). O NMe OMe
306 V.N. Bulavka and O.N. Tolkachev THE SYNTHESIS OF ALKALOIDS OF THE GALANTHAMINE GROUP The first synthesis confirming the structure of galanthamine Galanthamine was isolated for the first time from Galanthus woronowii and its preliminary structure was proposed from data on the chemical degradation of its molecule using classical methods (Proskurnina and Yakovleva, 1952, 1955). The final confirmation of the structures of galanthamine, narwedine and lycoramine were made by their total synthesis. The first biomimetic route of (±)-2, and after its resolution, of (+)-1, (–)-1 and (–)-lycoramine synthesis, proposed by Barton and Kirby (1960, 1962), included the oxidation of diphenolic substrates such as O,Ndimethyl-norbelladine (6, R = Me), the biogenetic precursor of 1, or its derivatives (Figure 12.2). The synthesis was carried out starting from 4-hydroxybenzaldehyde (7) through cyanohydrine (8) and 4-hydroxyphenylacetic acid (9) (34%), which, after O-benzylation into 10 (67%), was converted into the acid chloride 11 (Figure 12.2). The coupling component was obtained from 3-benzyloxy-4-methoxybenzaldehyde (12) via the intermediate Schiff base (13), with a subsequent reduction to 3-benzyloxy-4-methoxy-N-methyl-benzylamine (14) (68% yield). With the acid chloride 11, the latter yielded the corresponding arylacetamide 15 (85%). The LiAlH4 reduction of 15 (88%) and Pd/C hydrogenolysis of the intermediate tertiary amine 16 produced the desired compound 6 in 76% yield. Oxidation with different agents produced the target ketone (±)-2 in very low yield (0.1–1.4%). The best results were obtained on K3 [Fe(CN) 6 ] oxidation (0.92–1.4%). The final LiAlH4 reduction afforded a mixture of (±)-1 and (±)-4 in the ratio 3:2 (ca. 100%), from which the first compound was isolated in crystalline form (39%). Aluminium isopropoxide reduction produced preferentially the epi-isomer (±)-4 (60%). The total yield of (±)-2 was 0.18%, and of (±)-1, only 0.07%. Also proposed was a method of conversion of the ketone (±)-2 into enantiomeric (–)-1 via a step of dynamic resolution of (±)-2 to (+)-2 in the presence of optically active additives (–)-1, (–)-4 or (–)-lycoramine, and the LiAlH4 reduction of (+)-2 to yield a mixture of (+)-1 and (+)-4. The latter were used for seeding during the conversion of the racemate to (–)-2. A similar LiAlH4 reduction of (–)-2 produced the target (–)-1 in 58% yield. The subsequent hydrogenation over Pd/C afforded (–)-lycoramine (Barton and Kirby, 1960, 1962). Recently, a modified version of the pilot plant method of dynamic resolution of (±)-narwedine has been applied (Shieh and Carlson, 1994; Czollner et al., 1998). Synthesis of narwedine via palladium-directed coupling The synthesis was modified by Holton et al. (1988) as follows (Figure 12.3). A hydroxy group in 3-hydroxy-4-methoxybenzaldehyde (18) was protected by the action of NaH in OP(NMe 2 ) 3 , N 2 , then MeSCH 2 Cl; the intermediate O-methylthiomethyl derivative (19) (Holton and Davis, 1977), on condensation with 4-hydroxyphenethylamine (17), gave the Schiff base 20, which, after NaBH 4 reduction to 21, hydroxymethylation and NaB(CN)H 3 reduction of 22, gave the N-methylderivative 23 in 90% overall yield. With LiPdCl 4 in MeOH-(i-Pr) 2 NH (–78 °C), 23 produced the palladium derivative (±)-24 as a diastereomeric mixture (95%). Oxidation with (CF 3 COO) 3 Tl (–10 °C) gave the expected compound (±)-25, which
Page 2 and 3:
Narcissus and Daffodil
Page 4 and 5:
Narcissus and Daffodil The genus Na
Page 6 and 7:
Contents Preface to the series vii
Page 8 and 9:
Preface to the series There is incr
Page 10 and 11:
Preface My interest in flower-bulb
Page 12 and 13:
Acknowledgements I would like to th
Page 14 and 15:
Gordon R. Hanks Crop and Weed Scien
Page 16 and 17:
Figures 1.1 The effect of bulb stor
Page 18 and 19:
Figures/Plates xvii 7.8 Accumulatio
Page 20:
Figures/Plates of different segment
Page 23 and 24:
2 G.R. Hanks Information about the
Page 25 and 26:
4 G.R. Hanks (1999), and the polysa
Page 27 and 28:
3 2 4 1 1 3 2 4 5 Flowering in 1976
Page 29 and 30:
8 G.R. Hanks Figure 1.6 Diagrammati
Page 31 and 32:
10 G.R. Hanks (Rees, 1969). When fl
Page 33 and 34:
12 G.R. Hanks Figure 1.8 The relati
Page 35 and 36:
14 G.R. Hanks root system of commer
Page 37 and 38:
16 G.R. Hanks Cremer, M.C., Beijer,
Page 39 and 40:
18 G.R. Hanks Roh, S.M. and Lee, J.
Page 41 and 42:
20 A.C. Dweck Figure 2.1 The narcis
Page 43 and 44:
22 A.C. Dweck Julians Hertfordshire
Page 45 and 46:
24 A.C. Dweck Herefordshire, if daf
Page 47 and 48:
26 A.C. Dweck the basis of an ancie
Page 49 and 50:
28 A.C. Dweck Britten, J. and Holla
Page 51 and 52:
3 Classification of the genus Narci
Page 53 and 54:
(1) (2) (3)
Page 55 and 56:
34 B. Mathew d. Section Jonquillae
Page 57 and 58:
36 B. Mathew N. cyclamineus DC. Flo
Page 59 and 60:
38 B. Mathew 1c. Section Ganymedes
Page 61 and 62:
40 B. Mathew umbel, fragrant; peria
Page 63 and 64:
42 B. Mathew recognition whatsoever
Page 65 and 66:
44 B. Mathew Note: N. elegans shows
Page 67 and 68:
46 B. Mathew ssp. praecox Gatt. and
Page 69 and 70:
(1) (2) (3) (4)
Page 71 and 72:
50 B. Mathew Table 3.1 Horticultura
Page 73 and 74:
52 B. Mathew RHS (1958) The Classif
Page 75 and 76:
54 G.R. Hanks grown for galanthamin
Page 77 and 78:
56 G.R. Hanks such as drying stores
Page 79 and 80:
Table 4.4 Areas of Narcissus cultiv
Page 81 and 82:
60 G.R. Hanks Following planting in
Page 83 and 84:
62 G.R. Hanks lost, resulting in th
Page 85 and 86:
64 G.R. Hanks pathogen-tested nucle
Page 87 and 88:
Figure 4.1 Mean monthly weather dat
Page 89 and 90:
68 G.R. Hanks (as well as natural e
Page 91 and 92:
70 G.R. Hanks compaction and its ef
Page 93 and 94:
72 G.R. Hanks bulbs with base rot)
Page 95 and 96:
74 G.R. Hanks Figure 4.3 Modern fro
Page 97 and 98:
76 G.R. Hanks caution. Higher rates
Page 99 and 100:
78 G.R. Hanks can also be prevented
Page 101 and 102:
80 G.R. Hanks Figure 4.4 A typical
Page 103 and 104:
82 G.R. Hanks Planting date The pra
Page 105 and 106:
84 G.R. Hanks Hanks and Jones, 1986
Page 107 and 108:
86 G.R. Hanks On sloping sites, gro
Page 109 and 110:
88 G.R. Hanks Insecticide and nemat
Page 111 and 112:
90 G.R. Hanks bulb growth, especial
Page 113 and 114:
92 G.R. Hanks Figure 4.7 Changes in
Page 115 and 116:
94 G.R. Hanks methods have been tes
Page 117 and 118:
96 G.R. Hanks the boxes, exiting at
Page 119 and 120:
98 G.R. Hanks usually collected in
Page 121 and 122:
100 G.R. Hanks respond to ethylene
Page 123 and 124:
102 G.R. Hanks using thiabendazole
Page 125 and 126:
104 G.R. Hanks required for the eff
Page 127 and 128:
106 G.R. Hanks and cross-cutting, s
Page 129 and 130:
108 G.R. Hanks In practice, moulds
Page 131 and 132:
110 G.R. Hanks that, with enterpris
Page 133 and 134:
112 G.R. Hanks Balatková, V., Tupy
Page 135 and 136:
114 G.R. Hanks (Narcissus pseudonar
Page 137 and 138:
116 G.R. Hanks Flint, G.J. (1983) E
Page 139 and 140:
118 G.R. Hanks Hanks, G.R. and Rees
Page 141 and 142:
120 G.R. Hanks Khatib, K. al (1996)
Page 143 and 144:
122 G.R. Hanks Luyten, I. (1935) Ve
Page 145 and 146:
124 G.R. Hanks O’Neill, T.M., Man
Page 147 and 148:
126 G.R. Hanks Ruamrungsri, S., Rua
Page 149 and 150:
128 G.R. Hanks Thompson, P.A. (1977
Page 151 and 152:
130 G.R. Hanks Williams, M. (1996)
Page 153 and 154:
132 J.B. Briggs Table 5.1 Typical g
Page 155 and 156:
134 J.B. Briggs Table 5.3 Actual gr
Page 157 and 158:
136 J.B. Briggs Table 5.4 Actual co
Page 159 and 160:
138 J.B. Briggs Table 5.5 Capital c
Page 161 and 162:
140 J.B. Briggs ADAS (1987a) Narcis
Page 163 and 164:
142 J. Bastida and F. Viladomat Fig
Page 165 and 166:
Table 6.1 Narcissus alkaloid struct
Page 167 and 168:
Table 6.1b Continued Alkaloid name
Page 169 and 170:
Table 6.1d Tazettine type O O R1 R2
Page 171 and 172:
Table 6.1f Continued MeO Alkaloid n
Page 173 and 174:
Table 6.2 Continued Species* Alkalo
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
162 J. Bastida and F. Viladomat Tab
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
Page 193 and 194:
Table 6.3 Continued Alkaloid* Formu
Page 195 and 196:
Table 6.3 Continued Alkaloid* Formu
Page 197 and 198:
176 J. Bastida and F. Viladomat Tab
Page 199 and 200:
178 J. Bastida and F. Viladomat Cri
Page 201 and 202:
180 J. Bastida and F. Viladomat It
Page 203 and 204:
Page 205 and 206:
184 J. Bastida and F. Viladomat is
Page 207 and 208:
186 J. Bastida and F. Viladomat and
Page 209 and 210:
Table 6.4 Continued Alkaloid Activi
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
196 J. Bastida and F. Viladomat tac
Page 219 and 220:
198 J. Bastida and F. Viladomat Ang
Page 221 and 222:
200 J. Bastida and F. Viladomat Boi
Page 223 and 224:
202 J. Bastida and F. Viladomat lyc
Page 225 and 226:
204 J. Bastida and F. Viladomat Fug
Page 227 and 228:
206 J. Bastida and F. Viladomat Han
Page 229 and 230:
208 J. Bastida and F. Viladomat Kin
Page 231 and 232:
210 J. Bastida and F. Viladomat of
Page 233 and 234:
212 J. Bastida and F. Viladomat Sp
Page 235 and 236:
214 J. Bastida and F. Viladomat Wil
Page 237 and 238:
216 C. Codina and, consequently, hi
Page 239 and 240:
218 C. Codina easily lost on transf
Page 241 and 242:
220 C. Codina they might be more su
Page 243 and 244:
222 C. Codina µ g/g FW µ g/g FW 3
Page 245 and 246:
224 C. Codina Kinetin As observed i
Page 247 and 248:
226 C. Codina Table 7.3 Total produ
Page 249 and 250:
228 C. Codina Accumulation of alkal
Page 251 and 252:
230 C. Codina Accumulation of alkal
Page 253 and 254:
232 C. Codina Effect on growth and
Page 255 and 256:
234 C. Codina mg/g DW mg/g DW 0.90
Page 257 and 258:
236 C. Codina mg/g DW mg/g DW 1.4 1
Page 259 and 260:
238 C. Codina mg/g DW mg/g DW 1.5 1
Page 261 and 262:
240 C. Codina Hanks, G.R. and Jones
Page 263 and 264:
8 Narcissus and other Amaryllidacea
Page 265 and 266:
244 O.A. Cherkasov and O.N. Tolkach
Page 267 and 268:
Page 269 and 270:
Page 271 and 272:
Page 273 and 274:
Page 275 and 276: 254 O.A. Cherkasov and O.N. Tolkach
Page 277 and 278: 9 Studies on galanthamine extractio
Page 279 and 280: 258 M. Kreh Table 9.1 Results of ga
Page 281 and 282: 260 M. Kreh relation to the qualita
Page 283 and 284: 262 M. Kreh Figure 9.3 Galanthamine
Page 285 and 286: 264 M. Kreh 2.0 flower 2 1 3 4 0 10
Page 287 and 288: 266 M. Kreh • High purity of the
Page 289 and 290: 268 M. Kreh fraction of Narcissus
Page 291 and 292: H O MeO O MeO H H HO H (1) (3) + 2
Page 293 and 294: 272 M. Kreh Gorinova, N.I., Atanass
Page 295 and 296: 274 R.M. Moraes (Katz and Taneck, 1
Page 297 and 298: 276 R.M. Moraes bulbs of many Narci
Page 299 and 300: 278 R.M. Moraes Galanthamine conten
Page 301 and 302: 280 R.M. Moraes Table 10.2 The effe
Page 303 and 304: 282 R.M. Moraes years, a yield of 1
Page 305 and 306: 284 R.M. Moraes Kosley, R.W., Jr.,
Page 307 and 308: 11 Extraction and quantitative anal
Page 309 and 310: 288 N.P.D. Nanayakkara and J.K. Bas
Page 317 and 318: Table 11.1 GC and HPLC procedures f
Page 319 and 320: Table 11.1 Continued References Det
Page 325: 12 Synthesis of galanthamine and re
Page 329 and 330: 308 V.N. Bulavka and O.N. Tolkachev
Page 353 and 354: 13 Compounds from the genus Narciss
Page 355 and 356: 334 D. Brown with neostigmine the a
Page 357 and 358: 336 D. Brown Absorption Galanthamin
Page 359 and 360: 338 D. Brown Metabolism and excreti
Page 361 and 362: 340 D. Brown were internationally i
Page 363 and 364: 342 D. Brown cortex and hippocampus
Page 365 and 366: 344 D. Brown reasoned that the effi
Page 367 and 368: 346 D. Brown Galanthamine causes br
Page 369 and 370: 348 D. Brown (1994) go on to mentio
Page 371 and 372: 350 D. Brown (Punto Toro and Rift V
Page 373 and 374: 352 D. Brown Furusawa, E., Lum, M.K
Page 375 and 376: 354 D. Brown Snorrason, E. and Stef
Page 377 and 378:
356 D. Brown examination of a brain
Page 379 and 380:
358 D. Brown A successful cholinerg
Page 381 and 382:
Table 14.2 Summary of human trials
Page 383 and 384:
362 D. Brown statistically signific
Page 385 and 386:
364 D. Brown ( Jann, 1998); see Tab
Page 387 and 388:
366 D. Brown REFERENCES Bartus, B.T
Page 389 and 390:
368 D. Brown Wilcock, G.K., Scott,
Page 391 and 392:
370 K. Ingkaninan, H. Irth and R. V
Page 393 and 394:
Page 395 and 396:
Page 397 and 398:
Page 399 and 400:
Page 401 and 402:
16 Narcissus lectins Els J.M. Van D
Page 403 and 404:
382 E.J.M. Van Damme and W.J. Peuma
Page 405 and 406:
Page 407 and 408:
Page 409 and 410:
Page 411 and 412:
Page 413 and 414:
17 Narcissus in perfumery HISTORY C
Page 415 and 416:
394 C. Remy Figure 17.2 Flower coll
Page 417 and 418:
Figure 17.3 Narcissus flowers sprea
Page 419 and 420:
398 C. Remy CONCLUSION The use of n
Page 421 and 422:
400 C.G. Julian and P.W. Bowers Fig
Page 423 and 424:
Page 425 and 426:
Page 427 and 428:
406 C.G. Julian and P.W. Bowers sym
Page 429 and 430:
19 Review of pharmaceutical patents
Page 431 and 432:
410 J.R. Murray to certain RNA viru
Page 433 and 434:
412 J.R. Murray occurs in a two-pha
Page 435 and 436:
414 J.R. Murray cognitive function
Page 437 and 438:
416 J.R. Murray given at a time bet
Page 439 and 440:
418 J.R. Murray Hofmannor, D., Mosc
Page 441 and 442:
420 Index Backache, 403 Bacterial d
Page 443 and 444:
422 Index Divisions (classification
Page 445 and 446:
424 Index Leaf numbers, 11 Leaf sco
Page 447 and 448:
426 Index Poet’s cultivars, 34 Po
Page 449:
428 Index Subgenus (taxonomy); Ajax
show all

Narcissus and Daffodil

Create successful ePaper yourself

Delete template?

Save as template?