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中草药垂盆草(Sedum sarmentosum Bunge)和三尖杉〔Cephalotaxus sinensis(Rehd.et Wils.)Li〕有效成分研究国内已进行多年,从垂盆草中提取的垂盆草甙是治疗肝炎的有效成份,由于该成分在垂盆草中含量极微,要大量提取提供临床使用很难,困此,国内不少化学、药学工作者试图合成垂盆草甙,均未取得成功,笔者在前人研究的基础上,进行了试探性的研究。设计了三条路线:①以氯乙醇作原料,羟基用THP保护,氯用碘化钠中碘负离子置换形成碘化物,二步反应产率为51％。将碘化物做成Wittig盐备用。由于缺丁基锂试剂,反应未能进行下去,笔者认为此路线成功可能性很大。②以丁炔二醇为原料,THP单边保护羟基,产率为46％,用锂铝氢和碘低温还原三键,得碘代反式双键,,该产物中的碘与CuCN反应,碘被CN~-取代,产率为98％。结构鉴定正在进行中。③仍以丁炔二醇为原料,经催化氢化得丁烯二醇,后将二羟基酰化、溴加成、氰基取代等反应,所得产物产率很低(30％),与①②相比不优化,高三尖杉酯碱(Homoharringtonine)和三尖杉酯碱(Harringtonine)是从三尖杉中提取得到的两种抗癌有效成分,经我国20多年临床应用证明,高三尖杉酯碱和三尖彬酯碱已成为目前治疗非淋巴性白血病的首选药物。国内不少学者从不同途径出发,实现了半合成,但要推上工业?
Sedum sarmentosum Bunge and Cephalotaxus sinensis (Rehd.et Wils.) Li active ingredient research has for many years, from sarmentosum sarmentosum extracted from the active ingredient is the treatment of hepatitis , Because of the content of subsoil in sarmentosum micro, to provide a large number of clinical use is difficult to extract, sleepy, many domestic chemical, pharmaceutical workers trying to synthesize sage glycosides, were not successful, the author in previous studies Based on the tentative research. Three routes were designed: (1) Chloroethanol was used as raw material and hydroxyl was protected by THP. Chloride was replaced by iodide anion in sodium iodide to form iodide. The yield of the two-step reaction was 51%. Iodide made of Wittig salt spare. Due to a lack of butyllithium reagent, the reaction failed to go on, I believe that this route a great possibility of success. ② to butynediol as raw material, THP unilateral protection of hydroxyl, the yield was 46%, with lithium aluminum hydride and iodine reduction three key to give iodine trans double bond, the product of iodine and CuCN reaction, Iodine was replaced by CN ~ - and the yield was 98%. Structural identification is in progress. ③ still butynediol as raw material, the catalytic hydrogenation of butylene glycol, after dihydroxy acylation, bromine addition, cyano substitution reaction, the resulting product yield is very low (30%), and ① ② phase Homoharringtonine and Harringtonine, two anti-cancer active ingredients extracted from Cephalotaxus, have been proved to be more effective than more than 20 years of clinical application in our country. Homoharringtonine and Harringtonine, And Sanxian Bin ester base has become the drug of choice for the treatment of non-lymphoid leukemia. Many domestic scholars set out from different ways to achieve a semi-synthetic, but to push the industry?