TY - JOUR
T1 - The mechanism of carboxylative cyclization of propargylamine by N-heterocyclic carbene complexes of Au(I).
AU - Davis, Jack V.
AU - Gamage, Mohan M.
AU - Guio, Oswaldo
AU - Bayrakdar, Tahani A.C.A.
AU - Nolan, Steven P.
AU - Temprado, Manuel
AU - Captain, Burjor
AU - Hoff, Carl D.
N1 - Funding Information:
The authors dedicate this paper to Professor László Kollár. We wish to thank the Department of Energy (DOE-BES-DE-SC0019456), the Ministerio de Economía y Competitividad, Spain (CTQ2016-80600-P), Special Research Fund (BOF) of Ghent University (starting and project grants to SPN) and VITO for a studentship to TACAB. Umicore AG is acknowledged for generous gifts of materials.
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2021/2/15
Y1 - 2021/2/15
N2 - The complex [Au(IPr)(2-oxazolidinone)] (1 = IKa) was prepared from reaction of [Au(IPr)Cl] (2), K2CO3, and propargyl amine (PPA). Kinetic studies have been performed for acid cleavage of 1 to yield the oxazolidinone product and an [Au(IPr)(X)] adduct. The fastest rates of cleavage were found to occur for the hydrogen chloride salt of PPA (PPA-HCl) and for the CO2 adduct of PPA, PPA-CO2 = the carbamic acid (CA). This transformation was studied as a function of [CA], pressure of CO2 as well as temperature. Detailed computational studies support the formation of a key intermediate and are also in agreement with a rapid carbonylation/decarbonylation reaction. The computed reactions mechanisms for addition of PPA-HCl and CA are also presented as well as the crystal structure of 1.
AB - The complex [Au(IPr)(2-oxazolidinone)] (1 = IKa) was prepared from reaction of [Au(IPr)Cl] (2), K2CO3, and propargyl amine (PPA). Kinetic studies have been performed for acid cleavage of 1 to yield the oxazolidinone product and an [Au(IPr)(X)] adduct. The fastest rates of cleavage were found to occur for the hydrogen chloride salt of PPA (PPA-HCl) and for the CO2 adduct of PPA, PPA-CO2 = the carbamic acid (CA). This transformation was studied as a function of [CA], pressure of CO2 as well as temperature. Detailed computational studies support the formation of a key intermediate and are also in agreement with a rapid carbonylation/decarbonylation reaction. The computed reactions mechanisms for addition of PPA-HCl and CA are also presented as well as the crystal structure of 1.
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U2 - 10.1016/j.jorganchem.2020.121583
DO - 10.1016/j.jorganchem.2020.121583
M3 - Article
AN - SCOPUS:85098493625
VL - 934
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
M1 - 121583
ER -