利用甾体皂甙元降解废弃物合成维生素E侧链及其相关化合物
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摘要
我们课题组发展的双氧水洁净氧化降解甾体皂甙元的方法,不仅避免了传统铬酐降解法的苛刻反应条件和严重的重金属污染,而且还提高了降解反应的收率,同时,还可以从降解废液中回收含有手性甲基的小分子,以它们作为手性源,可以方便地合成多种含有手性甲基的有机化合物分子。
本论文的工作就是以降解甾体皂甙元所回收到的(R)-4-甲基戊内酯2-108和(R,R)-4-甲基-2-羟基戊内酯2-106为原料,合成一些含有手性甲基的天然产物分子或其片段。论文工作主要包括以下几个部分：
1、为了有效的利用(R)-4-甲基戊内酯2-108和(R,R)-4-甲基-2-羟基戊内酯2-106,发展几个比较成熟的小分子化合物的制备方法,把它们转化成为稳定存在的小分子,作为合成其它化合物起始原料。
2、以(R)-5-叔丁基二甲基硅氧基-4-甲基戊酸甲酯2-105为原料,通过LiAlH4还原,碘代,格氏试剂偶联,脱TBS保护,再经过碘代,wittig反应,氢化等8步反应,以52%的总收率合成维生素E侧链(2R,6R)-2,6,10-三甲基十一醇2-53。
3、以(2R,4R)-2,5-二-叔丁基二甲基硅氧基-4-甲基戊酸甲酯3-35为原料探索合成(+)-Menthofuran3-1的路线。已完成(+)-Menthofuran结构中六员环的构建,呋喃环的构建还在探索中……
The method for degradation of steroidal sapogenins with hydrogen peroxide developed by our research group is milder and less contaminative than the classic one using CrO3 as the degradation reagent. This new method also improved the yield of the degradation and at the same time, optically pure (R)-4-methylvalerolactone, a new chiral source which can be used in the synthesis of many natural products containing chiral methyl was obtained from the residue of degradation of steroidal sapogenins.
This dissertation dealed with synthesis of some natural products containing chiral methyl in their molecules using (R)-4-methylvalerolactone and (R,R)-4-methyl-2-hydroxylvalerolactone as the starting material.
There are four parts in this dissertation.
1. A few mature ways of preparation t of small molecule compounds were developed for making good use of (R)-4-methylvalerolactone and (R,R)-4-methyl-2-hydroxylvalerolactone. They are transformed into stable small molecules, which can be used as starting materials in the synthesis of other compounds.
2. Using (R)-methyl-5-(tert-butyldimethylsilyloxy)-4-methylpentanoate as the starting material, through the LiAlH4 reduction, iodization, coupling, deprotection of TBS, iodization, wittig reaction, and hydrogenation eight-step reaction,52% total yield, optical active vitamin side chain has been synthesized.
3. Using (2R,4R)-5-((tert-butyldimethylsilyl)oxy)-4-methylpentane-1,2-diol as the starting material, exploring a route to the synthesis of (+)-Menthofuran. Six-membered ring has been built, the synthesis of five-membered ring is under exploration..
本论文的工作就是以降解甾体皂甙元所回收到的(R)-4-甲基戊内酯2-108和(R,R)-4-甲基-2-羟基戊内酯2-106为原料,合成一些含有手性甲基的天然产物分子或其片段。论文工作主要包括以下几个部分：
1、为了有效的利用(R)-4-甲基戊内酯2-108和(R,R)-4-甲基-2-羟基戊内酯2-106,发展几个比较成熟的小分子化合物的制备方法,把它们转化成为稳定存在的小分子,作为合成其它化合物起始原料。
2、以(R)-5-叔丁基二甲基硅氧基-4-甲基戊酸甲酯2-105为原料,通过LiAlH4还原,碘代,格氏试剂偶联,脱TBS保护,再经过碘代,wittig反应,氢化等8步反应,以52%的总收率合成维生素E侧链(2R,6R)-2,6,10-三甲基十一醇2-53。
3、以(2R,4R)-2,5-二-叔丁基二甲基硅氧基-4-甲基戊酸甲酯3-35为原料探索合成(+)-Menthofuran3-1的路线。已完成(+)-Menthofuran结构中六员环的构建,呋喃环的构建还在探索中……
The method for degradation of steroidal sapogenins with hydrogen peroxide developed by our research group is milder and less contaminative than the classic one using CrO3 as the degradation reagent. This new method also improved the yield of the degradation and at the same time, optically pure (R)-4-methylvalerolactone, a new chiral source which can be used in the synthesis of many natural products containing chiral methyl was obtained from the residue of degradation of steroidal sapogenins.
This dissertation dealed with synthesis of some natural products containing chiral methyl in their molecules using (R)-4-methylvalerolactone and (R,R)-4-methyl-2-hydroxylvalerolactone as the starting material.
There are four parts in this dissertation.
1. A few mature ways of preparation t of small molecule compounds were developed for making good use of (R)-4-methylvalerolactone and (R,R)-4-methyl-2-hydroxylvalerolactone. They are transformed into stable small molecules, which can be used as starting materials in the synthesis of other compounds.
2. Using (R)-methyl-5-(tert-butyldimethylsilyloxy)-4-methylpentanoate as the starting material, through the LiAlH4 reduction, iodization, coupling, deprotection of TBS, iodization, wittig reaction, and hydrogenation eight-step reaction,52% total yield, optical active vitamin side chain has been synthesized.
3. Using (2R,4R)-5-((tert-butyldimethylsilyl)oxy)-4-methylpentane-1,2-diol as the starting material, exploring a route to the synthesis of (+)-Menthofuran. Six-membered ring has been built, the synthesis of five-membered ring is under exploration..
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