期刊
JOURNAL OF CATALYSIS
卷 405, 期 -, 页码 322-332出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2021.12.011
关键词
Hydrocarboxylation; alpha,beta-Unsaturated carboxylic acids; Formic acid; CO surrogate; Hydrogen source; Multifunctional ligand; Co-catalytic effect
资金
- National Natural Science Foundation of China [21972045, 22172052]
The hydrocarboxylation of terminal alkynes with formic acid was achieved using a multifunctional ligand modified Pd-catalyst. The multifunctional ligand played a crucial role in activating the substrates and ensuring high yields with regioselectivity.
Hydrocarboxylation of terminal alkynes with formic acid (FA) was accomplished over a multifunctional ligand (L2) modified Pd-catalyst, advantageous with 100% atom-economy, free use of CO and H2O, mild reaction conditions, and high yields (56-89%) of alpha,beta-unsaturated carboxylic acids with 100% regioselectivity to the branched ones. The multifunctional ligand of L2 as a zwitterion salt containing the phosphino-fragment (-PPh2), Lewis acidic phosphonium cation and sulfonate group (-SO3), was constructed on the skeleton of 1.1'-binaphthyl-2.2'-diphenyl phosphine (BINAP) upon selective quaternization by 1,3-propanesultone. It was found that L2 conferred to the Pd-catalyst the co-catalytic effect, wherein the phosphino-coordinated Pd-complex was responsible for activation of all the substrates (including CO, FA and alkyne), and the incorporated phosphonium cation was responsible for synergetic activation of FA. The H-1 NMR spectroscopic analysis supported that FA was truly activated by the incorporated Lewis acidic phosphonium cation in L2 via acid-base pair interaction. The in situ FT-IR spectra demonstrated that, the presence of Ac2O and NaOAc additives in the catalytic amount could dramatically promote the in situ release of CO from FA, which was required to initiate the hydrocarboxylation. (C) 2021 Elsevier Inc. All rights reserved.
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