- Page 1: Università Degli Studi di Salerno
- 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 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
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2.2.ENANTIOSELECTIVE TOTAL SYNTHESI
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O 2.15 (S)-MeCBS reagent BH 3 THF T
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Reduction of the ester functionalit
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OH CHO 2.1 CHO MeO DCC DMAP CH 2Cl
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OH O 2.28 PPTS (6%), THF/MeOH (1:1)
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HO Synthesis of 1--p cumaroil poly
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HO Synthesis of hybrid structure 2
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2.3 TOTAL SYNTHESIS OF POLYGODIAL C
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2.4 ENANTIOSELECTIVE TOTAL SYNTHESI
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As previously described, the Diels
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In the scheme below (Scheme 2.18) i
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It has been proposed this following
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The decalinic backbone 2.60 is give
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HO O 2.7 2.59 CHO CHO OAc PO HO HO
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From a very complex mixture we have
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HO K 2CO 3, MeOH 60°C 92% OAc TBSO
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TBSO HF 48% CH 3CN rt 70% 2.77 OH H
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2.6 TOTAL SYNTHESIS OF POLYGODIAL C
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2.7.2. SYNTHESIS OF 1(R)HYDROXYPOLY
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(%) = 166(8), 149(100), 148(50), 13
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OTBS COOMe Compound 2.17 B: Rf = 0.
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OTBS COOMe COOMe Compound 2.19: Rf
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Hydrogenation of 2.18 (H2, Pd/C, Me
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flash-chromatography (40% - 60% die
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Compound 2.2: Rf = 0.57 (50% ethyl
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HO Compound 2.60 [Found: C, 73.13;
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stirred at room temperature for 1h.
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HO 2 3 14 1 15 4 5 6 13 10 11 Compo
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MHz):9.51 (1H, d, J = 4.4 Hz), 9.47
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CHAPTER 3 APPROACH TO THE SYNTHESIS
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In order to prepare the epoxypolyen
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2.65 OAc OAc AD-mix t-BuOH, H 2O, M
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3.2 A CONVERGENT SYNTHESIS OF EPOXY
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3.2.2 SYNTHETIC SECTION This sectio
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The mechanism proposed for this rea
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Once obtained this fragment 3.23 we
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O O O S O 3.24 OH Cl 2Pd(dppp) SupH
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It has been concluded that a sulfon
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HO O HO 3.3.2 SYNTHETIC SECTION As
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Many attempts were carried out, usi
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palladium (II) chloride), which gav
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Table 3.1 Exp H - eq T (°C) Time (
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O 3.34 O OEt SupH THF -10°C 75% SC
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O O O KHMDS PhN(Tf) 2 MeB(OH) 2 Pd(
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O O TBSCl, imidazole CH 3CN, 90°C
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O HO n=2 OH CHO SCHEME 3.35 HO CHO
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The resulting organic layers are wa
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SYNTHESIS OF ALLYLIC ALCOHOL 3.13 S
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ALLYL-ALLYL COUPLING To a stirred s
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DESULFONILATION OF 3.24 Without fur
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over 20 min, and the reaction mixtu
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O 3.33 OTf (m, 2H); 1.62 (s, 3H); 1
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O 5H); 1.31 (s, 3H); 1.27 (s, 3H).
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PREPARATION OF -KETO ESTER 3.41 A f
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SUZUKI CROSS COUPLING ON 3.43 Vinyl
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CHAPTER 4 BIOACTIVITY ASSAYS 163
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MeO A B C D HO AcO CHO CHO CHO CHO
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H 3CO O M O CHO CHO CHO CHO N - - 1
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Figure B Figure C Anti-proliferativ
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Department of Chemistry A new appro
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5.1 OUTLINE The amount of research
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H O Me H H OAc O Pyrethrosin 5.5 an
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Carpesium macrocephalum and Carpesi
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Me O O OH O O 5.17 O Et O O O Pseud
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O O O O MeO MeO OH HO O Taiwanin A
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The allergenic properties of -methy
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Me Me Me Me Me OPP OPP FPP a) Oxida
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CH3COSCoA + CH Glucose 3COCOOH HO H
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5.5.1 By Alkylidenation of -Butyrol
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Eschenmoser‟s salt can be employe
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Me H 5.46 OH CHO PH 3P O 5.47 CH 2C
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Cyclization of the optically active
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Finally, the classical Dreiding-Sch
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of [Ni(CO)2(PPh3)2] and proceeded b
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5.5.6 Radical Cyclization Approache
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The key was the use of diethyl phos
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expected -methylene lactone 5.85 in
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(EtO) 2P(O) O O O Me 5.90 O OH Me K
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6.1 C-H INSERTION WITH RHODIUM CARB
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This alternative approach offers ma
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6.1.3 Rh(II) Catalysts It has known
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Davies 163 [principally dirhodium(I
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electron-withdrawing groups (eg. CO
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General Mechanism Me Me Me E H H E
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6.3 RHODIUM (II) CHEMISTRY IN SYNTH
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Then, the same reaction has been ca
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6.49 OH O O HO P OEt OEt T3P DIPEA
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O O OH N 2 H O P 6.59 OEt OEt Rh 2(
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O O O O O DAG 6.68 OH O O OEt P OH
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Starting from L-valinol 6.75, a dia
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Cyclisation performed on cyclohexan
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R 1 H H O 6.90 (51%) H H 1) Rh 2(oc
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O O N 2 O EtO O O P O O OEt O O Rh
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6.5 -CONCLUSIONS A wide number of -
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6.6.2 General Procedure preparation
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P i BuO OEt Compound 4. Yellow oil.
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-CH2Ph), 1.25 (t, 3 J = 7.2 Hz, 6 H
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Compound 17. Yellow oil. 1 H NMR (4
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Compound 24. Yellow oil. 1 H NMR (4
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13 C NMR (100 MHz, CDCl3): δ = 169