インドールアルカロイド類の転換反応 (第4報) インドールアルカロイド合成におけるC/D環閉環反応の再検討並びにヘテロヨヒンビンAricineおよびReserpinineの合成

概要

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The C/D ring closing reaction of optically active 2,3-seco-2,3-dihydroakuammigine (II) with Hg (OAc)_2-EDTA・2Na was reinvestigated and the isolated products were found to be tetrahydroalstonine (III), insideheteroyohimbine (V), and insidedehydroyohimbine (VI). There was no evidence for the formation of akuammigine (V), and insidedehydroyohimbine (VI). There was no evidence for the formation of akuammigine (IV), different from that of Uskokovic using racemic compound (II) as the starting material. Modified Polonvski reaction of compound II N-oxide (IXa) gives IV, V, and a piperidine derivative Xb. Bond cleavage between N4 and C5 of compound (II) with carbobenzoxy chloride formed an urethane derivative (Xc) as a major product. Compound Xc yielded a piperidine derivative (Xa) by hydrogenolysis. On the other hand, pteropodine (Ia) was transformed to Xa via XIIIc, d. The synthesis of aricine (XIXa) and reserpinine (XIXb) using Xa was achieved by the usual method. Combination of these procedures forms a new general method to synthesize various kinds of aromatic substituted heteroyohimbinoid indole alkaloids.
社団法人日本薬学会の論文
1978-07-25