Abstract
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 with t1/2 42.5 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.
Original language | English (US) |
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Pages (from-to) | 10496-10497 |
Number of pages | 2 |
Journal | Journal of the American Chemical Society |
Volume | 125 |
Issue number | 35 |
DOIs | |
State | Published - Sep 3 2003 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry