Enantioselective Synthesis of Polyethers

描述(由申请人提供)：该计划将继续开发实用、灵活的策略，用于六至九元环醚的对映选择性合成，并将新策略应用于结构新颖和具有生物重要性的天然产物的全合成。在此研究过程中，将探索基于建立非环立体化学阵列然后闭环的环醚和碳环的不对称结构的新的合成技术。在下一批赠款期间，将完成短杆菌毒素A的全部合成。此外，还将继续研究合成山梨糖素A、短叶草醛、半短杆菌毒素B、硬藻素A、茶黄素A和维拉西林。还将准备这些天然产品的重要类似物。一种新型的1，1‘-二取代醚键的三组分组装、一种新的不对称乙酸酯羟醛和一种抗乙醇酸酯羟醛将被进一步开发和利用。二碘克莱森重排将被进一步发展，用于构建四元立体合成中心，并应用于野百合素A和维拉西林。将进行短杆菌毒素A、山梨糖素A、短链菌素A、石蒜素A和维拉西林的全合成。将研究合成环醚和碳环的新的对映选择性方法。

DESCRIPTION (provided by applicant): This program will continue to develop practical, flexible strategies for the enantioselective synthesis of six to nine membered ring ethers and apply the new strategies to the total synthesis of structurally novel and biologically important natural products. During the course of this investigation, new synthetic technologies will be explored for the asymmetric construction of cyclic ethers and carbocycles based on establishing acyclic stereochemical arrays followed by ring closure. During the next grant period the total synthesis of brevetoxin A will be completed. The synthesis of sorangicin A, brevenal, hemibrevetoxin B, sclerophytin A, brianthein A, and verillin will also be pursued. Important analogs of these natural products will also be prepared. A novel 3- component assembly of 1, 1'-disubstituted ether linkages, a new asymmetric acetate aldol, and an anti-glycolate aldol will be further developed and exploited. The dianioic Claisen rearrangement will be further developed for construction of quaternary stereogenic centers and applied to brianthein A and verillin. The total synthesis of brevetoxin A, sorangicin A, brevenal sclerophytin A, brianthein A and verillin will be carried out. New enantioselective methods for the synthesis of cyclic ethers and carbocycles will be investigated.