Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts
Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S.
American Association for the Advancement of Science (AAAS)
Published 2018
American Association for the Advancement of Science (AAAS)
Published 2018
| Publication Date: |
2018-03-06
|
|---|---|
| Publisher: |
American Association for the Advancement of Science (AAAS)
|
| Print ISSN: |
0036-8075
|
| Electronic ISSN: |
1095-9203
|
| Topics: |
Biology
Chemistry and Pharmacology
Geosciences
Computer Science
Medicine
Natural Sciences in General
Physics
|
| Keywords: |
Chemistry
|
| Published by: |
| _version_ | 1836398829216202752 |
|---|---|
| autor | Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. |
| beschreibung | Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules. |
| citation_standardnr | 6194179 |
| datenlieferant | ipn_articles |
| feed_id | 25 |
| feed_publisher | American Association for the Advancement of Science (AAAS) |
| feed_publisher_url | http://www.aaas.org/ |
| insertion_date | 2018-03-06 |
| journaleissn | 1095-9203 |
| journalissn | 0036-8075 |
| publikationsjahr_anzeige | 2018 |
| publikationsjahr_facette | 2018 |
| publikationsjahr_intervall | 7984:2015-2019 |
| publikationsjahr_sort | 2018 |
| publisher | American Association for the Advancement of Science (AAAS) |
| quelle | Science |
| relation | http://science.sciencemag.org/cgi/content/short/359/6379/1016?rss=1 |
| schlagwort | Chemistry |
| search_space | articles |
| shingle_author_1 | Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. |
| shingle_author_2 | Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. |
| shingle_author_3 | Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. |
| shingle_author_4 | Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. |
| shingle_catch_all_1 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts Chemistry Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules. Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. American Association for the Advancement of Science (AAAS) 0036-8075 00368075 1095-9203 10959203 |
| shingle_catch_all_2 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts Chemistry Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules. Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. American Association for the Advancement of Science (AAAS) 0036-8075 00368075 1095-9203 10959203 |
| shingle_catch_all_3 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts Chemistry Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules. Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. American Association for the Advancement of Science (AAAS) 0036-8075 00368075 1095-9203 10959203 |
| shingle_catch_all_4 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts Chemistry Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules. Hong, S. Y., Park, Y., Hwang, Y., Kim, Y. B., Baik, M.-H., Chang, S. American Association for the Advancement of Science (AAAS) 0036-8075 00368075 1095-9203 10959203 |
| shingle_title_1 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| shingle_title_2 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| shingle_title_3 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| shingle_title_4 | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| timestamp | 2025-06-30T23:33:18.011Z |
| titel | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| titel_suche | Selective formation of {gamma}-lactams via C-H amidation enabled by tailored iridium catalysts |
| topic | W V TE-TZ SQ-SU WW-YZ TA-TD U |
| uid | ipn_articles_6194179 |