10 0 - EleA@UniSA - Università degli Studi di Salerno

Index
ABSTRACT……………………………………………………………………………………………………………………………8
CHAPTER 1
Introduction…………………………………………………………………………………………………………………………10
1.1 Bioactive Terpenoidic Dialdehydes: An Overview……………………………………………………………11
1.2 Sesquiterpenoidic Dialdehydes……………………………………………………………………………………….14
1.3 Spongiane And Ent-Isocopalane Dialdehydes………………………………………………………………….21
1.4 Scalarane Dialdehydes…………………………………………………………………………………………………….24
1.5 Bioactivity: Structural Requirements And TRP Receptors Interaction………………………………28
CHAPTER 2
1.5.1 Early Investigations On The Mechanism Of Action Of Bioactive Dialdehydes………30
1.5.2 TRP Receptors Ion Channels………………………………………………………………………………37
1.5.3 From Hot Chili Pepper To Thermoreception: TRPV1 Vanilloid Receptor…………….43
1.5.4 The Discover Of TRPA1 Receptor…………………………………………………………………………47
Total Synthesis Of Sesquiterpenoidic Dialdehydes …………………………………………………………………50
2.1 Outline …………………………………………………………………………………………………………………………… 51
2.2 Enantioselective Total Synthesis Of Polygodial C1 Derivatives…………………….......................53
2.2.1 Synthesis Of Polygodial C-1 Analogues: Retrosynthetic Analysis………………………….53
2.2.2 Synthesis Of 1-(R)-Hydroxypolygodial………………………………………………………………….54
2.2.3 Synthesis Of 1--(Methoxycinnamoyl)Polygodial And Preparation Of Other C-1 Acyl
Derivatives…………………………………………………………………………………………………………58
2.3 Total Synthesis Of Polygodial C1 Derivatives–Concusions……………………………………………….67
2.4 Enantioselective Total Synthesis Of C-3 Polygodial Derivatives……………………………………….69
2.4.1 A New Straightforward Synthetic Strategy: Cyclisation By Free Radical
Chemistry….………………………………………………………………………………………………………..69
2.5 Total Synthesis Of 3-Hydroxypolygodial And Its Analogues……………………………………………….78
2.5.1 Retrosyntetic Scheme………………………………………………………………………………………….78
2.5.2 Synthesis Of 3--Hydroxypolygodial…………………………………………………………………….79
2.5.3 Direct Acylation Of C3-OH:Synthesis Of 3- Acethoxypolygodial And 3-(P-
Methoxycinnamoil)Polygodial……………………………………………………………………………85
2.6 Total Synthesis Of Polygodial C3 Derivatives–Concusions…………………………………………………87
2.7 Experimental…………………………………………………………………………………………………………………….88
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