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Isogatholactone 1.19 O O FIGURE 1.13 -Spongia zimocca H H OAc O OAc Spongiane Skeleton (1.20) CHO R 1-21;R= CHO 1.22;R= CHO ent isocopalane skeleton FIGURE 1.14 -Some natural occurring spongiane and ent-isocopalane compounds 22
From Spongia officinalis (Figure 1.15) in the 1999 has been isolated ent- Isocopal- 12-ene- 15,16-dialdehyde 1.5, a C-20 diterpenoid presents a trans- fused tricyclic system with a 1,4-dialdehyde function, adjacent to the double bond of the cyclohexene ring. 19 (Figure 1.16) FIGURE 1.15 - Spongia officinalis CHO CHO FIGURE 1.16 - ent-Isocopal- 12-ene- 15,16-dialdehyde from Spongia officinalis 1.5 23
Page 1 and 2: Università Degli Studi di Salerno
Page 3 and 4: Ci sono momenti in cui la vita rega
Page 5 and 6: CHAPTER 3 Approach To The Synthesis
Page 7 and 8: LIST OF ABBREVIATION Cl2Pd(dppp) 1,
Page 9 and 10: In the chapter three an approach to
Page 11 and 12: 1.1 BIOACTIVE TERPENOIDIC DIALDEHYD
Page 13 and 14: 1.1 CHO CHO OAc 1.2 CHO CHO CHO CHO
Page 15 and 16: CHO FIGURE 1.3- Polygonum hydropipe
Page 17 and 18: AcO 1.9 O OAc SCHEME 1.1 CHO 1.1 CH
Page 19 and 20: HO O O 1.12 CHO CHO FIGURE 1.9- 1--
Page 21: 1.4 HO CHO CHO CHO CHO 1.16 HO 1.17
Page 25 and 26: The B-ring functionalization has al
Page 27 and 28: It has been found that some sponges
Page 29 and 30: 1.1 1.4 CHO CHO CHO CHO CHO CHO 1.8
Page 31 and 32: This is what could be happen when a
Page 33 and 34: OAc OAc CHO N CHO H 2N COOH 1.6 1.4
Page 35 and 36: 1.4 OAc Scalaradial (1.6) not activ
Page 37 and 38: It has been supposed that some natu
Page 39 and 40: a change in ionic permeability and
Page 41 and 42: FIGURE 1.28 Activation of TRP recep
Page 43 and 44: Our research has been focused in pa
Page 45 and 46: HO HO N S HN Capsazepine (1.50) FIG
Page 47 and 48: When the assays were carried out on
Page 49 and 50: It has been shown that this rare ir
Page 51 and 52: 2.1 OUTLINE In this chapter the tot
Page 53 and 54: 2.2.ENANTIOSELECTIVE TOTAL SYNTHESI
Page 55 and 56: O 2.15 (S)-MeCBS reagent BH 3 THF T
Page 57 and 58: Reduction of the ester functionalit
Page 59 and 60: OH CHO 2.1 CHO MeO DCC DMAP CH 2Cl
Page 61 and 62: OH O 2.28 PPTS (6%), THF/MeOH (1:1)
Page 63 and 64: HO Synthesis of 1--p cumaroil poly
Page 65 and 66: HO Synthesis of hybrid structure 2
Page 67 and 68: 2.3 TOTAL SYNTHESIS OF POLYGODIAL C
Page 69 and 70: 2.4 ENANTIOSELECTIVE TOTAL SYNTHESI
Page 71 and 72: As previously described, the Diels
Page 73 and 74:
In the scheme below (Scheme 2.18) i
Page 75 and 76:
It has been proposed this following
Page 77 and 78:
The decalinic backbone 2.60 is give
Page 79 and 80:
HO O 2.7 2.59 CHO CHO OAc PO HO HO
Page 81 and 82:
From a very complex mixture we have
Page 83 and 84:
HO K 2CO 3, MeOH 60°C 92% OAc TBSO
Page 85 and 86:
TBSO HF 48% CH 3CN rt 70% 2.77 OH H
Page 87 and 88:
2.6 TOTAL SYNTHESIS OF POLYGODIAL C
Page 89 and 90:
2.7.2. SYNTHESIS OF 1(R)HYDROXYPOLY
Page 91 and 92:
(%) = 166(8), 149(100), 148(50), 13
Page 93 and 94:
OTBS COOMe Compound 2.17 B: Rf = 0.
Page 95 and 96:
OTBS COOMe COOMe Compound 2.19: Rf
Page 97 and 98:
Hydrogenation of 2.18 (H2, Pd/C, Me
Page 99 and 100:
flash-chromatography (40% - 60% die
Page 101 and 102:
Compound 2.2: Rf = 0.57 (50% ethyl
Page 103 and 104:
HO Compound 2.60 [Found: C, 73.13;
Page 105 and 106:
stirred at room temperature for 1h.
Page 107 and 108:
HO 2 3 14 1 15 4 5 6 13 10 11 Compo
Page 109 and 110:
MHz):9.51 (1H, d, J = 4.4 Hz), 9.47
Page 111 and 112:
CHAPTER 3 APPROACH TO THE SYNTHESIS
Page 113 and 114:
In order to prepare the epoxypolyen
Page 115 and 116:
2.65 OAc OAc AD-mix t-BuOH, H 2O, M
Page 117 and 118:
3.2 A CONVERGENT SYNTHESIS OF EPOXY
Page 119 and 120:
3.2.2 SYNTHETIC SECTION This sectio
Page 121 and 122:
The mechanism proposed for this rea
Page 123 and 124:
Once obtained this fragment 3.23 we
Page 125 and 126:
O O O S O 3.24 OH Cl 2Pd(dppp) SupH
Page 127 and 128:
It has been concluded that a sulfon
Page 129 and 130:
HO O HO 3.3.2 SYNTHETIC SECTION As
Page 131 and 132:
Many attempts were carried out, usi
Page 133 and 134:
palladium (II) chloride), which gav
Page 135 and 136:
Table 3.1 Exp H - eq T (°C) Time (
Page 137 and 138:
O 3.34 O OEt SupH THF -10°C 75% SC
Page 139 and 140:
O O O KHMDS PhN(Tf) 2 MeB(OH) 2 Pd(
Page 141 and 142:
O O TBSCl, imidazole CH 3CN, 90°C
Page 143 and 144:
O HO n=2 OH CHO SCHEME 3.35 HO CHO
Page 145 and 146:
The resulting organic layers are wa
Page 147 and 148:
SYNTHESIS OF ALLYLIC ALCOHOL 3.13 S
Page 149 and 150:
ALLYL-ALLYL COUPLING To a stirred s
Page 151 and 152:
DESULFONILATION OF 3.24 Without fur
Page 153 and 154:
over 20 min, and the reaction mixtu
Page 155 and 156:
O 3.33 OTf (m, 2H); 1.62 (s, 3H); 1
Page 157 and 158:
O 5H); 1.31 (s, 3H); 1.27 (s, 3H).
Page 159 and 160:
PREPARATION OF -KETO ESTER 3.41 A f
Page 161 and 162:
SUZUKI CROSS COUPLING ON 3.43 Vinyl
Page 163 and 164:
CHAPTER 4 BIOACTIVITY ASSAYS 163
Page 165 and 166:
MeO A B C D HO AcO CHO CHO CHO CHO
Page 167 and 168:
H 3CO O M O CHO CHO CHO CHO N - - 1
Page 169 and 170:
Figure B Figure C Anti-proliferativ
Page 171 and 172:
Department of Chemistry A new appro
Page 173 and 174:
5.1 OUTLINE The amount of research
Page 175 and 176:
H O Me H H OAc O Pyrethrosin 5.5 an
Page 177 and 178:
Carpesium macrocephalum and Carpesi
Page 179 and 180:
Me O O OH O O 5.17 O Et O O O Pseud
Page 181 and 182:
O O O O MeO MeO OH HO O Taiwanin A
Page 183 and 184:
The allergenic properties of -methy
Page 185 and 186:
Me Me Me Me Me OPP OPP FPP a) Oxida
Page 187 and 188:
CH3COSCoA + CH Glucose 3COCOOH HO H
Page 189 and 190:
5.5.1 By Alkylidenation of -Butyrol
Page 191 and 192:
Eschenmoser‟s salt can be employe
Page 193 and 194:
Me H 5.46 OH CHO PH 3P O 5.47 CH 2C
Page 195 and 196:
Cyclization of the optically active
Page 197 and 198:
Finally, the classical Dreiding-Sch
Page 199 and 200:
of [Ni(CO)2(PPh3)2] and proceeded b
Page 201 and 202:
5.5.6 Radical Cyclization Approache
Page 203 and 204:
The key was the use of diethyl phos
Page 205 and 206:
expected -methylene lactone 5.85 in
Page 207 and 208:
(EtO) 2P(O) O O O Me 5.90 O OH Me K
Page 209 and 210:
6.1 C-H INSERTION WITH RHODIUM CARB
Page 211 and 212:
This alternative approach offers ma
Page 213 and 214:
6.1.3 Rh(II) Catalysts It has known
Page 215 and 216:
Davies 163 [principally dirhodium(I
Page 217 and 218:
electron-withdrawing groups (eg. CO
Page 219 and 220:
General Mechanism Me Me Me E H H E
Page 221 and 222:
6.3 RHODIUM (II) CHEMISTRY IN SYNTH
Page 223 and 224:
Then, the same reaction has been ca
Page 225 and 226:
6.49 OH O O HO P OEt OEt T3P DIPEA
Page 227 and 228:
O O OH N 2 H O P 6.59 OEt OEt Rh 2(
Page 229 and 230:
O O O O O DAG 6.68 OH O O OEt P OH
Page 231 and 232:
Starting from L-valinol 6.75, a dia
Page 233 and 234:
Cyclisation performed on cyclohexan
Page 235 and 236:
R 1 H H O 6.90 (51%) H H 1) Rh 2(oc
Page 237 and 238:
O O N 2 O EtO O O P O O OEt O O Rh
Page 239 and 240:
6.5 -CONCLUSIONS A wide number of -
Page 241 and 242:
6.6.2 General Procedure preparation
Page 243 and 244:
P i BuO OEt Compound 4. Yellow oil.
Page 245 and 246:
-CH2Ph), 1.25 (t, 3 J = 7.2 Hz, 6 H
Page 247 and 248:
Compound 17. Yellow oil. 1 H NMR (4
Page 249 and 250:
Compound 24. Yellow oil. 1 H NMR (4
Page 251:
13 C NMR (100 MHz, CDCl3): δ = 169
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