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生物重要的天然产物的全合成。在本研究过程中，将探索新的合成技术，为环醚和碳环的不对称结构的基础上建立无环立体化学阵列，然后闭环。在下一个资助期内，将完成短杆菌毒素A的全合成。还将继续合成sorangicin A、brevenal、hemibrevetoxin B、sclerophytin A、brianthein A和verillin。还将制备这些天然产物的重要类似物。一种新的三组分组装的1，1 '-二取代醚键，一种新的不对称乙酸酯羟醛和一种反乙醇酸酯羟醛将被进一步开发和利用。双阴离子Claisen重排将进一步发展用于构建四级立体中心，并应用于brianthein A和verillin。本论文将进行短梗霉毒素A、囊兰菌素A、短梗霉硬植素A、brianthein A和verillin的全合成。本论文将研究对映选择性合成环醚和碳环化合物的新方法。

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.