Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes
Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label...
| Main Authors: | , , , |
|---|---|
| Format: | Online |
| Language: | English |
| Published: |
Nature Publishing Group
2016
|
| Online Access: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4906407/ |
| id |
pubmed-4906407 |
|---|---|
| recordtype |
oai_dc |
| spelling |
pubmed-49064072016-06-24 Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes Krause, Thilo Baader, Sabrina Erb, Benjamin Gooßen, Lukas J. Article Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label ‘amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. Nature Publishing Group 2016-06-10 /pmc/articles/PMC4906407/ /pubmed/27282773 http://dx.doi.org/10.1038/ncomms11732 Text en Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
| repository_type |
Open Access Journal |
| institution_category |
Foreign Institution |
| institution |
US National Center for Biotechnology Information |
| building |
NCBI PubMed |
| collection |
Online Access |
| language |
English |
| format |
Online |
| author |
Krause, Thilo Baader, Sabrina Erb, Benjamin Gooßen, Lukas J. |
| spellingShingle |
Krause, Thilo Baader, Sabrina Erb, Benjamin Gooßen, Lukas J. Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| author_facet |
Krause, Thilo Baader, Sabrina Erb, Benjamin Gooßen, Lukas J. |
| author_sort |
Krause, Thilo |
| title |
Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| title_short |
Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| title_full |
Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| title_fullStr |
Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| title_full_unstemmed |
Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| title_sort |
atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes |
| description |
Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label ‘amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. |
| publisher |
Nature Publishing Group |
| publishDate |
2016 |
| url |
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4906407/ |
| _version_ |
1613594172264022016 |