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  • Chapter Two Biomimetic Partial Synthesis Of
    CHAPTER TWO BIOMIMETIC PARTIAL SYNTHESIS OF VALPARICINE AND APPARICINE 2.1 Introduction 2.1.1 Alkaloids of Kopsia arborea A total of 62 alkaloids were isolated from the stem-bark and leaves of Kopsia arborea of which 25 are new alkaloids. Among the alkaloids isolated are valparicine (28),26,27 pericine (31),26,28,29 pericidine (32),30,31 arbophylline (33),32 arboricine (34),30,33 arboricinine (35),30,33 arboflorine (36),30,34 arboloscine (37),30,31 and mersicarpine (38).35 14 The compounds of interest to this research are valparicine (28) and pericine (31). Valparicine (28) was isolated from the stem-bark extract of K. arborea in trace amount. It represents the first member of the pericine-type alkaloids, characterized by a 16-22 exocyclic double bond, in which bond-formation has occurred between C-3 and C-7.26 Preliminary tests indicated that valparicine (28) showed strong cytotoxic effects −1 against human KB cells (IC50 < 5 μgmL ). Valparicine (28) was obtained as a colorless oil, with [α]D −40 (c 0.22, CHCl3). The UV spectrum (228 and 297 nm) indicated the presence of an unsubstituted indolenine chromophore. The EIMS of 28 showed a molecular ion at m/z 276, which 13 analyzed for C19H20N2, differing from pericine (31) by loss of two hydrogens. The C NMR spectrum gave a total of 19 carbon resonances (one methyl, five methylenes, seven methines, and six quaternary carbons) in agreement with the molecular formula. In addition to the six carbon resonances readily attributable to the aromatic moiety, and the imine resonance at δC 186.4, two other downfield quaternary resonances were observed at δC 139.2 and 144.6.
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