Halichondrin B: synthesis of the C(1)-C(15) subunit.
Halichondrin B: synthesis of the C(1)-C(15) subunit.
复制标题
软海绵素 B：C(1)-C(15) 亚基的合成。
DOI：
10.1021/jo000140r
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
Klovning,JJ
中科院分区：
文献类型：
--
作者：
Burke,SD;Jung,KW;Lambert,WT;Phillips,JR;Klovning,JJ
A short and efficient synthesis of the C(1)−C(15) subunit of halichondrin B in its natural configuration is described. The polycyclic caged ketal3, containing nine asymmetric centers, is prepared in 14 steps from α-d-glucoheptonic acid γ-lactone (7). Key steps in the two similar routes described include EtMgBr-promoted pinacol ring expansions of hydroxy mesylates23and34, intramolecular Michael additions of29and37, and a one-pot, HF-induced conversion of4to3involving in situ silyl ether cleavage, acetal hydrolysis, Michael addition, and caged ketal formation. Alternative protocols for carbinol inversion at C(11), one early and one late in the synthetic sequence, are also described.
