Studies On The Synthesis Of Marine Products 15-oxopuupehenol And Strongylin A

The vast ocean is rich in species,and with the development and utilization of advanced technologies,more and more marine organisms are known and un-derstood.Many types of natural products are also found in abundant marine life species.Terpenoids are a very important group of natural products.Such natural products are favored by researchers because of their novel structure,unique spa-tial configuration,and because of their various biological activities,such as an-ti-tumor,anti-virus,anti-cancer,and anti-fungal.Therefore,it is desirable and valuable to develop effective and flexible methods to synthesize biologically ac-tive marine natural products and their anal ogs from the point of view of medicine/pharmaceutical chemistry.15-oxopuunehenol and strongyin A are both a terpe-noid compound extracted from deep-sea sponges.Because of their unique rigid structure and remarkable antitumor and antiviral pharmacologica l activity,they have received considerable potential as a new therapeutic agent.Value.In this paper,the synthesis of 15-oxopuunehenol and strongyin A,a marine natural product,is designed based on the research progress at home and abroad and re-lated organic chemical mechanisms.The main research work is as follows:1.The total synthesis of 15-oxopuuhehenol mainly includes the following steps:After the previous research on the compound and the structural character-istics of the compound,the compound 15-oxopuuhehenol reverse synthesis analysis,the compound can be divided into two fragments for double ring halves Terpene fragments and benzene ring fragments,the bicyclic sesquiterpene part is obtained from the commercially available commercially available perilla lactone through hydroxylation reaction,sodium periodate oxidation reaction,lithium aluminum hydride reduction reaction to obtain benz oyl threonaldehyde,and then with p-toluene The reaction of sulfonyl hydrazide can obtain the fragment of fragrant hydrazone with terpene group.The benzene ring is partially protected by1,2,4-pyrogallol through acetal and methoxy,and the benzene ring is replaced by iodine to obtain another fragment.The two fragments are coupled through the carbon migration under the palladium catalyst to achieve the coupling,and the DDQ oxidation reaction is used to construct the key synthetic intermediate,the carbonyl group is first constructed at the C-15 position,then the intramolecular Michael cyclization is closed under the action of Na OH,and the protective group is removed to achieve the goal Total synthesis of natural product molecules.Af-ter 12 steps of reaction,a total yield of 17%gives marine natural product15-oxopuuhehenol.2.The total synthesis of Strongylin A mainly includes the following steps:similar to the synthesis of the previous compounds,using the same steps to ob-tain hydrazone compounds and functionalized aromatic compounds,the two（triphenylphosphine）palladium catalyzed completion of the two fragments In combination with triethylsilane,the reductive isomerization of the allyl alcohol was obtained to obtain the enene terpene compound.A to tal of 6 steps of reaction yielded key intermediates with higher yields.In the final step,the reaction with BF₃·Et₂O did not occur the migration of the agglomerates,but the ring-closed product was obtained with a total yield of 25%.