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Synlett 2021; 32(07): 713-717
DOI: 10.1055/a-1326-6973
DOI: 10.1055/a-1326-6973
letter
Ynoate-Initiated Selective C–N Esterification of Tertiary Amines under Transition-Metal and Oxidant-Free Conditions
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (22078192, 31702070), the Natural Science Foundation of Shanghai (19ZR1437900), and Shanghai University of Engineering Science (E3-0903-19-01366).
Abstract
An efficient and selective method for metal- and oxidant-free deaminated esterification of tertiary amines is presented. In this protocol, ynoates play a key role to activate the Csp3–N bond through a process of in situ generation of zwitterionic salts. The transformations show that Csp3–N bond in the zwitterionic species has a lower dissociation energy than Csp2–N bond, leading to break preferentially and be trapped by carboxylic acids to generate the corresponding products in moderate to good yield.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1326-6973.
- Supporting Information
Publikationsverlauf
Eingereicht: 24. Oktober 2020
Angenommen nach Revision: 01. Dezember 2020
Accepted Manuscript online:
01. Dezember 2020
Artikel online veröffentlicht:
05. Januar 2021
© 2020. Thieme. All rights reserved
Georg Thieme Verlag KG
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General Procedure for the Synthesis of Dibenzyl 2,6-Pyridine-dicarboxylate (4aa)
A mixture of pyridine-2,6-dicarboxylic acid (2a, 83.5 mg, 0.5 mmol, 1.0 equiv) and ethyl propiolate (3a, 157 mg, 1.6 mmol, 3.2 equiv) was added a 10 mL tube along with a magnetic stir bar, and then 2 mL 1,4-dioxane was added. The tube was stirred and refluxed in oil bath at 80 °C. Subsequently, N,N-dimethylbenzylamine (1a, 202 mg, 1.5 mmol, 3 equiv) solved in 1 mL 1,4-dioxane was added to the tube slowly for 10 min. And the tube was stirred again and refluxed at 80 °C for 12 h. After the removal of the volatiles in vacuo, the crude residue was loaded on a silica gel (100–200 mesh) column and flashed with 20% ethyl acetate in petroleum ether to afford the desired product 4aa in 81% yield.
Dibenzyl 2,6-Pyridine-dicarboxylate (4aa)
White solid; 140 mg, 81% yield; mp 111–113 ℃. 1H NMR (400 MHz, CDCl3): δ = 8.27 (d, J = 7.8 Hz, 2 H), 7.97 (t, J = 7.8 Hz, 1 H), 7.48 (m, J = 7.7 Hz, 4 H), 7.42–7.31 (m, 6 H), 5.45 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 163.90, 148.01, 137.79, 134.97, 128.27, 127.88, 127.58, 67.26.
Dibenzyl 2,6-Furan-dicarboxylate (4ab)
White solid; 144 mg, 86% yield; mp 73–75 ℃. 1H NMR (400 MHz, CDCl3): δ = 7.45–7.33 (m, 10 H), 7.20 (d, J = 4.1 Hz, 2 H), 5.36 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 157.39, 146.36, 134.75, 128.30, 127.97, 118.22, 66.66.
Dibenzyl 2,6-Thiophene-dicarboxylate (4ac)
White solid; 101 mg, 57% yield; mp 56–58 ℃. 1H NMR (400 MHz, CDCl3): δ = 7.76 (s, 2 H), 7.46–7.33 (m, 10 H), 5.35 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 161.38, 139.01, 135.35, 133.25, 128.60, 128.28, 67.30. HRMS (EI): m/z calcd for C20H16O4S [M]+: 352.0764; found: 352.0765.