Kinetic analysis of a reactive model enediyne

M. F. Semmelhack; R. Sarpong

doi:10.1002/poc.798

Kinetic analysis of a reactive model enediyne

M. F. Semmelhack, R. Sarpong

Chemistry

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

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 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).

Original language	English (US)
Pages (from-to)	807-813
Number of pages	7
Journal	Journal of Physical Organic Chemistry
Volume	17
Issue number	9
DOIs	https://doi.org/10.1002/poc.798
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

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10.1002/poc.798

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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).",

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AB - 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).

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KW - Calicheamicin

KW - Enediyne model

KW - Hydrogen atom abstraction

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Kinetic analysis of a reactive model enediyne

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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