99(P20) ラジカル反応を利用する(+)-リコリンの合成研究(ポスター発表の部)

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概要

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• Lycorine (1) is one of representative components in Amaryllidaceae alkaloids, which possesses many interesting and potential biological activities such as antineoplastic and antiviral activity. Moreover, since the structure contains four contiguous chiral carbon centers (all trans) and a double bond, it is an attractive target for exploring new synthetic methodology. Although a number of synthetic studies on racemic lycorine have been reported to date, only one report on the synthesis of (+)-lycorine (1) by Schultz and co-workers have appeared. Our strategy for a total synthesis of (+)-lycorine (1) consists of construction of B and C rings in lycorane by stepwise diastereoselective radical cyclization reaction. At first, we synthesized 2-methyllycoranes (2a,b) as a model experiment. Thus, we prepared several radical precursors (10-14) from 6-bromopiperonyl alcohol (3) and chiral imide (6) in seven to eight steps. Radical reaction of 10-14 afforded cyclized products (16a-19a and 16b-19b) in a ratio of 1.08 to 1.70. The cyclized product (16a) having desired stereochemistry was converted to imidazolide (24), radical reaction of which proceeded in 6-endo trig. cyclization to furnish optically active 2-methyl-α-(2a) and 2-methyl-β-lycoranes (2b). In a similar way, radical precursors (27-29) for a total synthesis of (+)-lycorine were synthesized from 6-iodopiperonyl alcohol (24) and 6. Among radical reaction of 27-29, 29 afforded a mixture of desired cyclized product (32a) and its diastereomer (32b) in the highest ratio (2.0: 1). Furthermore, reduction followed by methanolysis of 32a,b furnished chromatographically separable amino alcohols (33a,b). Compound (33a) was converted to radical precursors (39L,H), radical reaction of which proceeded smoothly to give functionalized lycoranes (40L,H). Transformation of 40L,H to (+)-1 is now in progress.

• 天然有機化合物討論会の論文
• 1998-08-31

著者

• 星野 修

  東京理科大学薬学部

• 甲斐 裕一郎

  東理大薬

• 石崎 幸

  東京理科大学薬学部

• 石崎 幸

  東理大薬

• 星野 修

  東理大薬

• 星野 修

  Faculty Of Pharmaceutical Sciences Science University Of Tokyo

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