Myers, Andrew G. and Harrington, Philip M. and Kwon, Byoung-Mog (1992) Evidence for aminoglycoside participation in thiol activation of neocarzinostatin chromophore. Synthesis and reactivity of the epoxy dienediyne core. Journal of the American Chemical Society, 114 (3). pp. 1086-1087. ISSN 0002-7863. doi:10.1021/ja00029a046. https://resolver.caltech.edu/CaltechAUTHORS:20180801-113954345
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180801-113954345
Abstract
The reaction of the chromophore subunit (1) of the natural antitumor antibiotic neocarzinostatin with methyl thioglycolate produces an NMR-observable intermediate, assigned as 2, which decays with a half-life of ~2 h at -38 °C to form the putative biradical 3. While the latter rearrangement is striking, perhaps no less so is the thiol addition step (1 → 2), which occurs readily at -70 °C in acetic acid-tetrahydrofuran (1:9, t_(1/2) ≃ 1.5 h, 0.2 M thiol). Reported herein are (1) the assembly of the full core functionality of neocarzinostatin chromophore in a synthetic system and (2) the preparation of a nonbasic derivative of the chromo-phore itself. Experiments with these synthetic materials provide strong evidence that thiol activation of 1 is facilitated dramatically through participation of the carbohydrate amino group as an internal base.
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Additional Information: | © 1992 American Chemical Society. Received October 17, 1991. Generous support from the National Institutes of Health, the David and Lucile Packard Foundation, the Sterling Drug Company, the Upjohn Company, Sandoz Pharmaceuticals Corporation, and Pfizer Inc. is gratefully acknowledged. We are indebted to Kayaku Co., Ltd. for neocarzinostatin powder. | ||||||||||||||
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Issue or Number: | 3 | ||||||||||||||
DOI: | 10.1021/ja00029a046 | ||||||||||||||
Record Number: | CaltechAUTHORS:20180801-113954345 | ||||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180801-113954345 | ||||||||||||||
Official Citation: | Evidence for aminoglycoside participation in thiol activation of neocarzinostatin chromophore. Synthesis and reactivity of the epoxy dienediyne core. Andrew G. Myers, Philip M. Harrington, and Byoung Mog Kwon. Journal of the American Chemical Society 1992 114 (3), 1086-1087. DOI: 10.1021/ja00029a046 | ||||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
ID Code: | 88457 | ||||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||||
Deposited By: | Tony Diaz | ||||||||||||||
Deposited On: | 01 Aug 2018 18:57 | ||||||||||||||
Last Modified: | 16 Nov 2021 00:27 |
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