Cochlearol A的合成和Sinensilactam A等灵芝杂萜的不对称合成研究

	Cochlearol A的合成和Sinensilactam A等灵芝杂萜的不对称合成研究; Studies on the Synthesis of Cochlearol A and Asymmetric Synthesis of Sinensilactam A and Other Meroterpenoids from Ganoderma Lucidum
	樊会兰
导师	秦红波
摘要	Three chapters are included in this thesis: In chapter 1, the progress on the synthesis of meroterpenoids from Ganoderma species was reviewed. The chapter 2 mainly demonstrated the research of (±)-Cochlearol A's synthesis. In the first route, after the successful construction of A and B rings, we planned to oxidize and break the double bond in the five membered ring of substrate 2-6, and then constructed the C and D rings. But the problem we were facing was that the double bond in the five membered ring of coumpound 2-6 was very stable, and we had tried many conditions without success, so we suspended this route. Next, we continued the progress in the synthesis of (±)-Cochlearol A by coumpound 2-17. After many attempts, finally, compound 2-35 was synthesized by Michael addition of compound 2-17 with methyl acrylate and Friedel-Crafts reaction in TfOH. Then we got the key intermediate compound 2-43 by DIBAL-H selective reduction; DMP oxidation; OsO4-mediated dihydroxylation and Acetal reaction in p-TsOH. The key to this route was the efficient construction of the benzocyclohexene structure in TfOH, with 90% yield. The chapter 3 mainly demonstrated the divergent asymmetric synthesis of several meroterpenoids from Ganoderma such as (+)-SinensilactamA. We use commercially available 2-oxocyclopentane carboxylate and 3-bromopropyne for alkylation, and then biocatalytic reduction of the alkylation product by baker's yeast, then the common intermediate compound 3-15 was obtained through four steps of reaction. Subsequently, the asymmetric synthesis of (+)-Sinensilactam A and other six compounds was completed by using a divergent synthesis strategy with 99% ee. This synthetic route featured a two-phase strategy: firstly, we commenced our synthetic efforts with alkylation product 3-36 which was transformed to enantiopure compound 3-38 by using a known bioloenzymatic process, and then the common intermediate compound 3-15 was synthesized in four consecutive steps. Secondly, early-stage rapid construction of a common planar tricyclic intermediate followed by highly selective late-stage transformationed into various Ganoderma meroterpenoids, key to the strategy were different epoxy opening approach by aryl or double bond of styrene rapid construction of a common planar tricyclic intermediate. (-)-Lingzhiol had been accomplished in 9 steps and 2.2 % overall yield; (+)-Lingzhilactone B was 12 steps and 2.8% overall yield; (+)-Lingzhilactone C was 13 steps and 2.5% overall yield; (+)-Sinensilactam A was 13 steps and 1.1% overall yield; (+)-epi-Lingzhilactone B was 10 steps and 5.2% overall yield; (+)-epi-Sinensilactam A was 11 steps and 2.3% overall yield.
	2020-08
文献类型	学位论文
条目标识符	http://ir.kib.ac.cn/handle/151853/74120
专题	昆明植物所硕博研究生毕业学位论文
推荐引用方式 GB/T 7714	樊会兰. Cochlearol A的合成和Sinensilactam A等灵芝杂萜的不对称合成研究, Studies on the Synthesis of Cochlearol A and Asymmetric Synthesis of Sinensilactam A and Other Meroterpenoids from Ganoderma Lucidum[D],2020.

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