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Another mechanism proposed for reaction between unsaturated dialdehydes and peptides was suggested by Fritz 30 this mechanism included both a pyrrole formation and a Michael-addition. (Scheme 1.3) 1.1 HO 1.13 CHO CHO CHO MeO 2C H 2N CHO H 2N Lys + + HS 1.38 Cys 1.36 SH SCHEME 1.3 Et 3N CDCl 3 The high reactivity of unsaturated dialdehydes toward primary amino groups is often proposed to explain their antibiotic activity and their enzyme inhibiting properties. In fact their reactivity towards primary amines in vivo may produce some of natural pyrrols (molliorins 1.41) which are co-isolated with the corresponding aldehyde scalaradial. This compound is formed in vivo in the sponge Cacospongia mollior, most probably by reaction with scalaradial 1.6 and ornitin 1.40. (Scheme 1.4) 30 Fritz, G.L; Mills, G.D.; Warthen, J.D.; Waters, R.M. J.Chem.Ecol. 1989, 15, 2607 HO HO N 1.39 1.37 S MeO 2C Lys N Cys 32 H S
OAc OAc CHO N CHO H 2N COOH 1.6 1.40 1.41 SCHEME 1.4 In conclusion the molecular mechanisms by which these type of compounds exert their bioactivities is still not unknown and many questions concerning the unsaturated dialdehyde and their activity remain. However it seems that the mechanism proposed by Sodano and co-workers has been confirmed from some evidences. In fact, when the dialdehyde moiety has a specific orientation with C-9 CHO oriented (instead of C-9 CHO the pyrrole compound is easily formed, because this orientation gives an optimal distance between the two groups, and allows easy reaction with bionucleophiles. This hypothesis could explain why polygodial is pungent to human tongue while is C-9 isomer is inactive. (Figure 1.23) . N AcO NH 2 33
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 and 22: 1.4 HO CHO CHO CHO CHO 1.16 HO 1.17
Page 23 and 24: From Spongia officinalis (Figure 1.
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: This is what could be happen when a
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
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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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10 0 - EleA@UniSA - Università degli Studi di Salerno

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