Fakultät Chemie, Technische Universität Dortmund, 44227 Dortmund, Germany.
Org Lett. 2010 Nov 19;12(22):5258-61. doi: 10.1021/ol1023008. Epub 2010 Oct 25.
The convergent enantioselective synthesis of a protected C1-C18 building block for the total synthesis of (-)-lytophilippine A was achieved. A catalytic asymmetric Gosteli-Claisen rearrangement and an Evans aldol reaction served as key C/C-connecting transformations during the assembling of the C1-C7 subunit (10 steps from 4, 29%). The synthesis of the C8-C18 segment was achieved utilizing d-galactose as inexpensive ex-chiral-pool starting material (15 steps, 15%). The merger of the subunits was accomplished by a remarkably efficient sequence consisting of esterification and ring-closing metathesis (five steps, 56%).
保护的 C1-C18 砌块的对映选择性汇聚合成，用于(-)-lytophilippine A 的全合成。在组装 C1-C7 亚基时，催化不对称的Gosteli-Claisen 重排和 Evans 羟醛缩合反应作为关键的 C/C 连接转化（从 4 开始的 10 步，收率 29%）。利用廉价的外消旋池起始原料 D-半乳糖（15 步，收率 15%）实现了 C8-C18 片段的合成。通过酯化和闭环复分解的高效序列（五步，收率 56%）完成了亚基的融合。
