Abstract
A model framework related to the calcheamicin family of enediyne toxins was evaluated in its reactivity toward cycloaromatization through the arene 1,4-diyl intermediates and hydrogen atom abstractions. The keto version 9 is relatively unreactive, with t1/2 = 1.5 h at 60°C. The product from hydride reduction of the ketone, alcohol 13b, is much more reactive, with t1/2 = 50 min at 0°C. In both cases, the rate of rearrangement is independent of the hydrogen atom donor, consistent with a rate-determining first step (cyclization).
Original language | English (US) |
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Pages (from-to) | 807-813 |
Number of pages | 7 |
Journal | Journal of Physical Organic Chemistry |
Volume | 17 |
Issue number | 9 |
DOIs | |
State | Published - Sep 2004 |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
Keywords
- Arene diradical
- Calicheamicin
- Enediyne model
- Hydrogen atom abstraction