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Kinetic analysis of a reactive model enediyne
Author(s) -
Semmelhack M. F.,
Sarpong R.
Publication year - 2004
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.798
Subject(s) - enediyne , chemistry , ketone , reactivity (psychology) , hydrogen atom , hydride , medicinal chemistry , hydrogen , alcohol , reactive intermediate , tributyltin hydride , stereochemistry , computational chemistry , organic chemistry , catalysis , medicine , alkyl , alternative medicine , pathology
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 t 1/2 = 1.5 h at 60°C. The product from hydride reduction of the ketone, alcohol 13b , is much more reactive, with t 1/2 =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). Copyright © 2004 John Wiley & Sons, Ltd.
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