Synlett
DOI: 10.1055/a-1319-6237
cluster
Radicals – by Young Chinese Organic Chemists

Neutral-Eosin Y-Catalyzed Regioselective Hydroacylation of Aryl Alkenes under Visible-Light Irradiation

Haiwang Liu
a  Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Republic of Singapore
,
Fei Xue
a  Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Republic of Singapore
b  Institute of Material Physics and Chemistry, College of Science, Nanjing Forestry University, Nanjing 210037, P. R. of China
,
Mu Wang
a  Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Republic of Singapore
,
Xinxin Tang
a  Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Republic of Singapore
,
Jie Wu
a  Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Republic of Singapore
c  National University of Singapore (Suzhou) Research Institute, 377 Lin Quan Street, Suzhou Industrial Park, Suzhou, Jiangsu, 215123, P. R. of China
› Author Affiliations
We are grateful for the financial support provided by the Ministry of Education (MOE) of Singapore (MOE2017-T2-2081), the National Natural Science Foundation of China (Grants 21871205, 22071170), and the National University of Singapore (Suzhou) Research Institute.


Abstract

Styrene derivatives were hydroacylated with exclusive anti-Markovnikov selectivity by using neutral eosin Y as a direct hydrogen-atom-transfer (HAT) catalyst under visible-light irradiation. Aldehydes and styrenes with various substituents were tolerated (>20 examples), giving the corresponding products in moderate to high yields. The key acyl radical intermediate was generated from a direct HAT process induced by photoexcited eosin Y. Subsequent addition to styrenes and a reverse HAT process generated the ketone products.

Supporting Information



Publication History

Received: 15 October 2020

Accepted after revision: 20 November 2020

Publication Date:
20 November 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
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  • 19 Ethyl 4-(3-Phenylpropanoyl)benzoate (8); Typical Procedure A 10 mL reaction tube equipped with a magnetic stirrer bar was charged with ethyl 4-formylbenzoate (1.0 mmol, 5.0 equiv), styrene (0.2 mmol, 1.0 equiv), eosin Y (0.01 mmol, 0.05 equiv), and PhF (4 mL). The tube was then sealed and degassed by using an argon balloon with a subsequent backfill with argon. The tube was then equipped with an argon balloon and placed under blue LEDs (3 m strip; 27 W) and irradiated for 72 h at 80 °C. The solvent was removed on a rotary evaporator under reduced pressure, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (15:1 to 1:1)] to give a colorless liquid; yield: 20.8 mg (36%). 1H NMR (500 MHz, CDCl3): δ = 8.14 0 8.08 (m, 2 H), 8.02–7.96 (m, 2 H), 7.34–7.27 (m, 2 H), 7.27–7.17 (m, 3 H), 4.40 (q, J = 7.1 Hz, 2 H), 3.39–3.28 (m, 2 H), 3.08 (t, J = 7.6 Hz, 2 H), 1.41 (t, J = 7.1 Hz, 3 H). 13C NMR (126 MHz, CDCl3): δ = 198.77, 165.76, 141.00, 139.97, 134.25, 129.82, 128.59, 128.43, 127.91, 126.26, 61.46, 40.83, 30.01, 14.29. GC/MS: m/z = 282.1 [M+].
  • 20 4-(3-Oxo-3-phenylpropyl)phenyl Acetate (15) Prepared by the typical procedure from PhCHO (1.0 mmol, 5.0 equiv), 4-vinylphenyl acetate (0.2 mmol, 1.0 equiv), and eosin Y (0.01 mmol, 0.05 equiv) as a colorless liquid; yield: 31.1 mg (58%). 1H NMR (400 MHz, CDCl3): δ = 8.00–7.91 (m, 2 H), 7.63–7.53 (m, 1 H), 7.51–7.41 (m, 2 H), 7.30–7.20 (m, 2 H), 7.05–6.94 (m, 2 H), 3.34–3.20 (m, 2 H), 3.06 (t, J = 7.6 Hz, 2 H), 2.28 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 199.03, 169.65, 149.01, 138.89, 136.82, 133.13, 129.42, 128.65, 128.04, 121.56, 40.37, 29.46, 21.13. HRMS (ESI): m/z [M + Na]+ calcd for C17H16NaO3: 291.0992; found: 291.0995.