A CO2-Catalyzed Transamidation Reaction
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A CO2-Catalyzed Transamidation Reaction. / Yang, Yang; Liu, Jian; Kamounah, Fadhil S.; Ciancaleoni, Gianluca; Lee, Ji-Woong.
In: The Journal of Organic Chemistry, Vol. 86, No. 23, 2021, p. 16867–16881.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - A CO2-Catalyzed Transamidation Reaction
AU - Yang, Yang
AU - Liu, Jian
AU - Kamounah, Fadhil S.
AU - Ciancaleoni, Gianluca
AU - Lee, Ji-Woong
PY - 2021
Y1 - 2021
N2 - Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2 as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular, N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2 atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2 in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2.
AB - Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2 as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular, N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2 atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2 in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2.
U2 - 10.1021/acs.joc.1c02077
DO - 10.1021/acs.joc.1c02077
M3 - Journal article
C2 - 34723529
VL - 86
SP - 16867
EP - 16881
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 23
ER -
ID: 284718529