资源化学研究进展

The Study of Resource Chemistry

本文总结了本课题组在资源化学领域的研究工作进展,内容涉及到天然资源化合物甾体皂甙元和非天然资源性化合物氟烷基磺酰氟的反应及其在有机合成中的应用。首先介绍了原子经济性地利用甾体皂甙元资源的策略与方法。为解决甾体皂甙元资源在工业利用过程产生的环境污染和资源浪费问题,我们发展了用30%双氧水代替铬酐氧化降解假甾体皂甙元的方法,使"百分之百"利用甾体皂甙元资源的理想成为现实。双氧水与乙酸原位产生的过氧酸直接氧化甾体皂甙元成为孕甾-16,20-二醇类化合物和4R-甲基-5羟基戊酸内酯,通过甾体皂甙元的非正常Baeyer-Villiger反应合成了甾体-16-羟基-22-内酯类化合物和3R-甲基-5羟基丁酸内酯。所获甾体中间体和带甲基侧链的双官能团手性试剂可应用于部分甾体药物、昆虫信息素、香料和天然产物的合成中。另外还介绍了利用甾体皂甙元完整骨架合成目标分子的资源性化合物利用策略。本文第二部分内容介绍了氟烷基磺酰氟资源利用的策略和方式。反应共生是我们提高氟烷基磺酰氟资源利用率的新思路,基于共生反应概念,研究了邻二醇环氧化反应、烯烃环氧化反应和碳正离子重排等反应与氟烷基磺酰氟水解反应的共生反应,并且介绍了其合成应用实例。

This review summarizes our research progress in resource chemistry,which related to the reaction of steroidal sapogenin（natural resource compound） and fluoroalkanosulfonyl fluoride（non-natural one） as well as their application in organic synthesis.The strategies and tactics of utilizing steroidal sapogenin in＂atom economy＂ way are introduced in the first paragraph.For solving the environmental pollution and resource waste generated in the industrial utilization of steroidal sapogenin,our group developed new method that using 30% commercial H2O2 instead of CrO3 to oxidize pseudo-sapogenin,which made it possible to the 100% utilization of the steroidal sapogenin resource.Direct oxidization of steroidal sapogenin with the per-acid generated in situ starting from 30% commercial H2O2and acid can produce pregna-16,20-diol type compounds and 4R-methyl δ-valerolactone.Iodine induced abnormal Baeyer-Villiger rearrangement of sapogenin provided steroidal 16-hydroxyl-22-lactone and 3Rmethyl γ-butyrolactone.All of their degraded products have been applied in the synthesis of some steroidal medicine,insect hormone,perfume and natural product.The strategy of using intact skeleton of steroidal sapogenin to synthesize target molecule are also described.In second paragraph,the strategies and tactics of utilizing fluoroalkanosulfonyl fluoride are introduced.To make reaction symbiosis is a new ideal in order to enhance the utilization ratio of the resource compounds.We explore symbiotic reactions of vicinal diol epoxidation,alkene epoxidation and carbocation rearrangement with fluoroalkanosulfonyl fluoride hydrolysis based on this concept.The synthetic application of such reactions is also presented in this review.