Conformational control in activation of an enediyne.
Conformational control in activation of an enediyne.
复制标题
烯二炔活化中的构象控制。
DOI：
10.1021/ja036763e
复制
发表时间：
2003
影响因子：
15
通讯作者：
Ho,DouglasM
中科院分区：
文献类型：
--
作者：
Semmelhack,MF;Wu,Lingyun;PascalJr,RobertA;Ho,DouglasM
In the bicyclo[7.3.1]tridec-4-ene-2,6-diyne framework characteristic of calicheamicin, DFT calculations predict that the chair conformer should be much more reactive toward cycloaromatization compared to the boat form. A functionalized derivative of this framework with an added two-atom bridge to enforce the boat conformation was synthesized and shown to be stable at 23 °C. Cleavage of the bridge releases the conformational lock and cycloaromatization proceeds witht1/242.5 min/23 °C, presumably through the chair conformation. This confirms the prediction based on computation and points to a new principle for triggering the enediyne toxins.
