Full text
| |
| Author(s): |
Emilio Carlos de Lucca Júnior
Total Authors: 1
|
| Document type: | Doctoral Thesis |
| Press: | Campinas, SP. |
| Institution: | Universidade Estadual de Campinas (UNICAMP). Instituto de Química |
| Defense date: | 2015-07-31 |
| Examining board members: |
Luiz Carlos Dias;
Gustavo Seoane Muniz;
Peter Bakuzis;
Fábio Cesar Gozzo;
Fernando Antonio Santos Coelho
|
| Advisor: | Luiz Carlos Dias |
| Abstract | |
MARINISPOROLIDE A: SYNTHETIC STRATEGY AND STRUCTURAL CONFIRMATION. This work describes our synthetic efforts that culminated with the first total synthesis of the oxopolyene macrolide marinisporolide A with a total of 56 steps and 25 steps for the longest linear sequence. Eleven C?C bonds were constructed in a very efficiently way and nine stereogenic centers were installed in a highly stereoselective manner. The key steps in this total synthesis are five aldol reactions (employed to form the C13?C14, C18?C19, C25?C26, C30?C31, and C32-C33 bonds), Julia?Kocie?ski olefination (to form the C22?C23 bond), a olefin cross-metathesis (to form the C10?C11 bond), a Stille cross-coupling (to form the C7?C8 bond), and a Horner?Wadsworth?Emmons olefination (responsible for building the C4?C5 bond). The greatest challenge in this total synthesis was the construction of the macrolactone. After numerous macrolactonization attempts, this challenge has been overcome by the use of the Masamune?Roush protocol for the Horner?Wadsworth?Emmons olefination (AU) | |
| FAPESP's process: | 11/06721-6 - Total synthesis of marinisporolide A |
| Grantee: | Emílio Carlos de Lucca Júnior |
| Support Opportunities: | Scholarships in Brazil - Doctorate |