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Synlett 2019; 30(11): 1366-1370
DOI: 10.1055/s-0037-1611538
DOI: 10.1055/s-0037-1611538
letter
Alcohol-Directed ortho-C–H Alkenylation
Authors
This work was financially supported by the National Natural Science Foundation of China (21825101, 21572004 for Y.H. and 21602007 for J.C.) and Shenzhen Science and Technology Innovation Commission (JCYJ20170818085510474, JCYJ20160226105602871, JCYJ20170818085438996).
Weitere Informationen
Publikationsverlauf
Received: 26. März 2019
Accepted after revision: 24. April 2019
Publikationsdatum:
21. Mai 2019 (online)
Abstract
We report a simple and mild dehydrogenative cross-coupling reaction of unprotected arylethanols and acrylates. Unlike the case of previous reactions, in which prior functionalization of the substrate with a metal-coordinating site was required, free primary, secondary, or tertiary hydroxy groups were found to be effective directing groups for the ortho-C–H palladation and subsequent olefination.
Key words
directing group - palladium catalysis - cross-coupling - C–H activation - arylethanols - acrylatesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611538.
- Supporting Information (PDF)
-
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- 17 3-[2-(2-Hydroxyethyl)phenyl]acrylate Esters 3a–q; General Procedure A flame-dried 15 mL microwave vial containing a stirrer bar was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol, 10 mol%), N-acetylglycine (4.7 mg, 0.04 mmol, 20 mol%), and Ag2CO3 (82.7 mg, 150 mol%, 0.3 mmol). (F3C)2CHOH (1.0 mL), the appropriate alcohol 1 (0.4 mmol), and the appropriate acrylate 2 (0.2 mmol) were then added sequentially. The vial was sealed with a rubber septum and then degassed and backfilled with argon three times. Under a positive argon pressure, the vial was clamped and sealed with an aluminum cap equipped with a septum, then heated at 90 °C for 15 h. The solvent was removed under vacuum, and the product was purified by flash column chromatography. Butyl (2E)-3-[2-(2-Hydroxyethyl)phenyl]acrylate (3a) Purified by flash column chromatography (silica gel, 15% EtOAc–hexanes) as a colorless oil; yield: 29.8 mg (60%). 1H NMR (400 MHz, CDCl3): δ = 8.02 (d, J = 15.8 Hz, 1 H), 7.60 (dd, J = 5.5, 3.2 Hz, 1 H), 7.44–7.16 (m, 4 H), 6.38 (d, J = 15.8 Hz, 1 H), 4.22 (t, J = 6.7 Hz, 2 H), 3.83 (d, J = 4.3 Hz, 2 H), 3.05 (t, J = 6.8 Hz, 2 H), 1.70 (dt, J = 14.6, 6.8 Hz, 2 H), 1.50–1.38 (m, 2 H), 0.97 (t, J = 7.4 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 167.46, 142.20, 138.39, 133.94, 131.16, 130.42, 127.44, 127.12, 120.25, 64.86, 63.67, 36.78, 31.08, 19.53, 14.08. HRMS (APCI): m/z [M + Na]+ calcd for C15H20NaO3: 271.1305; found: 271.1308.