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Synlett 2021; 32(08): 800-804
DOI: 10.1055/a-1387-5435
DOI: 10.1055/a-1387-5435
letter
Study on Palladium(II)-Catalyzed Mono-1-alkenylation of 9H-Carbazoles
We are grateful for financial support from the National Natural Science Foundation of China (NSFC-31800678), the Science and Technology Research Project in Shanxi Province (Nos. 201801D221062), the Shanxi Excellent Doctor Grant Award (No. SXYBKY201737, SXYBKY201706), the Science and Technology Innovation Project of Shanxi Agricultural University (No. 2017YJ38, 2017YJ41, ZDPY201606, ZDPY201708, ZDPY201803), Shanxi Science and Technology Research Project (201703d, 221008-4), and Science and Technology Innovation Project of Shanxi (2019L0374).
Abstract
A general and efficient method is reported for the direct mono-1-alkenylation of 9H-carbazole molecules with divalent palladium as a catalyst and an N-(2-pyridyl)sulfanyl directing group. This method also provides an efficient synthetic route for the synthesis of cross-dialkenylated carbazoles.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1387-5435.
- Supporting Information
Primary Data
- Primary Data
Primary data for this article are available online at https://zenodo.org/record/4633398 and can be cited using the following DOI: 10.5281/zenodo.4633398.
Publikationsverlauf
Eingereicht: 17. Dezember 2020
Angenommen nach Revision: 09. Februar 2021
Accepted Manuscript online:
09. Februar 2021
Artikel online veröffentlicht:
30. März 2021
© 2021. Thieme. All rights reserved
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1-Alkenyl-9H-carbazoles 3a–j; General Procedure A sealed tube containing 9-(2-pyridylsulfonyl)-9H-carbazole (1a; 0.2 mmol) and Pd(OAc)2 (5.0 mg, 10 mol%) was evacuated and filled with O2 gas by using an O2-containing balloon. HFIP (2 mL), the appropriate alkene (0.4 mmol), and TFA (0.4
mmol) were sequentially added from a syringe under O2, and the mixture was heated at 60 °C for 14–16 h until the reaction was complete
(TLC). The mixture was then allowed to cool to r.t., concentrated under reduced pressure,
diluted with EtOAc (30 mL), and washed with sat. aq NaHCO3 (3 × 2 mL). The combined organic phase was (Na2SO4) and concentrated under reduced pressure, and the residue was purified by flash chromatography.
Methyl (2E)-3-[9-(Pyridin-2-ylsulfonyl)-9H-carbazol-1-yl]acrylate (3a) Purified by flash column chromatography [silica gel,
PE–EtOAc (3:1)] as a white solid; yield: 37.0 mg (95%); mp 171–172 °C. IR (KBr): 3027,
2951, 1702, 1578, 1429, 1406, 1359, 1272, 1182, 1116, 1031, 956, 860, 752, 663, 586
cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.37 (d, J = 15.8 Hz, 1 H), 8.31 (d, J = 4.0 Hz, 1 H), 8.22 (d, J = 8.3 Hz, 1 H), 7.83–7.78 (m, 2 H), 7.74–7.70 (m, 2 H), 7.64 (d, J = 7.8 Hz, 1 H), 7.43–7.37 (m, 2 H), 7.32–7.27 (m, 2 H), 6.46 (d, J = 15.8 Hz, 1 H), 3.83 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 167.5, 154.5, 149.8, 144.0, 140.6, 139.3, 137.6, 130.1, 127.4, 126.0, 125.4,
125.2, 122.8, 121.1, 119.8, 118.5, 117.1, 51.7. HRMS (ESI): m/z [M + Na]+ calcd for C21H16N2NaO4S: 415.0723; found: 415.0721. Unsymmetrical Dialkenylated Carbazoles 3k–m; General Procedure A sealed tube was charged with the appropriate monoalkenylated carbazole 3 (0.2
mmol), Pd(OAc)2 (5.0 mg, 10 mol%), and K2S2O8 (108.0 mg, 0.4 mmol). DCE (2 mL) and the appropriate alkene (0.4 mmol) were added,
and the mixture was heated to 90 °C for 24–26 h until the reaction was complete (TLC).
The mixture was allowed to cool to r.t., diluted with EtOAc (50 mL), and washed with
H2O (3 × 5 mL). The combined organic phase was dried (Na2SO4) and concentrated under reduced pressure and purified by flash chromatography. Methyl (2E)-3-[8-[(1E)-3-(Dimethylamino)-3-oxoprop-1-en-1-yl]-9-(pyridin-2-ylsulfonyl)-9H-carbazol-1-yl]acrylate (3k) Purified by flash column chromatography [silica gel, PE–EtOAc (3:1)] as an oil; yield:
44.9 mg (92%). IR (KBr): 3394, 3189, 2921, 2850, 1708, 1646, 1465, 1419, 1371, 1263,
1168, 1110, 869, 794, 727, 642, 572 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.51 (d, J = 16.0 Hz, 1 H),
8.22–8.19 (m, 2 H), 7.66–7.62 (m, 2 H), 7.60–7.49 (m, 3 H), 7.38–7.30 (m, 3 H), 7.25–7.22
(m, 1 H), 7.05 (d, J = 15.6 Hz, 1 H), 6.54 (d, J = 16.0 Hz, 1 H), 3.88 (s, 3 H), 3.27 (s, 3 H), 3.11 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 167.3, 152.6, 149.1, 141.9, 141.4, 138.8, 137.0, 132.0, 131.7, 129.3, 127.9,
127.1, 126.8, 126.5, 125.9, 123.3, 121.0, 120.2, 118.8, 118.1, 51.9, 37.8, 35.9. HRMS
(ESI): m/z [M + Na]+ calcd for C26H23N3NaO5S: 512.1251; found: 512.1252. Methyl (2E)-3-(9H-carbazol-1-yl)acrylate (4a); Typical Procedure A suspension of 3a (39 mg, 0.1 mmol) and nonactivated Zn powder (325 mg, 5 mmol) in 1:1 THF–sat. aq
NH4Cl (4 mL) was stirred at 30 ℃ until the starting material was consumed (TLC). The
mixture was then filtered through a pad of Celite to remove the Zn powder, and the
filtrate was extracted with EtOAc (15 mL).
The extracts were washed with sat. aq NH4Cl and brine, and the combined organic phase was dried (Na2SO4) and concentrated. The residue was purified by flash chromatography [silica gel,
PE–EtOAc (4:1)] to give a light-yellow solid; yield: 24.1 mg (95%); mp 98–99 °C. IR
(KBr): 3355, 2123, 1707, 1325, 1173, 1028, 754, 602 cm–1. 1H NMR (400 MHz, DMSO): δ = 11.84 (s, 1 H), 8.31 (d, J = 16.0 Hz, 1 H), 8.20 (d, J = 7.6 Hz, 1 H), 8.14 (d, J = 7.8 Hz, 1 H), 7.85 (d, J = 7.5 Hz, 1 H), 7.59 (d, J = 8.1 Hz, 1 H), 7.51–7.40 (m, 1 H), 7.19–7.21 (m, 1 H), 6.82 (d, J = 16.0 Hz, 1 H), 3.79 (s, 3 H). 13C NMR (100 MHz, DMSO): δ = 167.5, 140.8, 140.6, 139.0, 126.6, 124.8, 124.3, 123.2,
122.6, 120.8, 119.7, 119.4, 117.7, 111.8, 51.9. HRMS (ESI): m/z [M + Na]+ calcd for C16H13NNaO2: 274.0838; found: 274.0834.
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