2026-04-13T06:18:25Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3058332026-01-15T14:12:32Zcom_2072_300912com_2072_4427col_2072_301309

RECERCAT author Correa, Arkaitz author León, Thierry author Martin, Ruben 2018-01-15T16:04:48Z2018-02-15T10:28:17Z2024-04-23T10:30:50Z 2018-01-15T16:04:48Z2018-02-15T10:28:17Z2024-04-23T10:30:50Z 2013 http://hdl.handle.net/2072/305833 https://doi.org/10.1021/ja410883p In recent years a significant progress has been made for the carboxylation of aryl and benzyl halides with CO2, becoming convenient alternatives to the use of stoichiometric amounts of well-defined metal species. Still, however, most of these processes require the use of pyrophoric and air-sensitive reagents and the current methods are mostly restricted to organic halides. Therefore, the discovery of a mild, operationally simple alternate carboxylation that occurs with a wide substrate scope employing readily available coupling partners will be highly desirable. Herein, we report a new protocol that deals with the development of a synergistic activation of CO2 and a rather challenging activation of inert C(sp2)–O and C(sp3)–O bonds derived from simple and cheap alcohols, a previously unrecognized opportunity in this field. This unprecedented carboxylation event is characterized by its simplicity, mild reaction conditions, remarkable selectivity pattern and an excellent chemoselectivity profile using air-, moisture-insensitive and easy-to-handle nickel precatalysts. Our results render our method a powerful alternative, practicality and novelty aside, to commonly used organic halides as counterparts in carboxylation protocols. Furthermore, this study shows, for the first time, that traceless directing groups allow for the reductive coupling of substrates without extended π-systems, a typical requisite in many C–O bond-cleavage reactions. Taking into consideration the limited knowledge in catalytic carboxylative reductive events, and the prospective impact of providing a new tool for accessing valuable carboxylic acids, we believe this work opens up new vistas and allows new tactics in reductive coupling events. eng © 2013 American Chemical Society Ni-catalyzed Carboxylation of C(sp2)– and C(sp3)–O Bonds with CO2 info:eu-repo/semantics/article URL https://recercat.cat/bitstream/2072/305833/2/Ni-cat%20carboxylation%20C-O%20bonds-final.pdf File MD5 25770775c1f69e3500afab85c2881e37 1079640 application/pdf Ni-cat carboxylation C-O bonds-final.pdf URL https://recercat.cat/bitstream/2072/305833/1/Ni-cat%20carboxylation%20C-O%20bonds-final.pdf.txt File MD5 1eaa116d3e0370344ef6f45a10b692e8 48318 text/plain Ni-cat carboxylation C-O bonds-final.pdf.txt