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Synlett 2021; 32(08): 800-804
DOI: 10.1055/a-1387-5435
letter

Study on Palladium(II)-Catalyzed Mono-1-alkenylation of 9H-Carbazoles

Dongdong Guo
a   College of Arts and Sciences, Shanxi Agricultural University, Taigu 030801, P. R. of China
b   Department of Chemistry & Materials Science, Northwest University, Xi’an 710069, P. R. of China
,
Bin Li
b   Department of Chemistry & Materials Science, Northwest University, Xi’an 710069, P. R. of China
,
Wenmei Gao
a   College of Arts and Sciences, Shanxi Agricultural University, Taigu 030801, P. R. of China
,
Wuxia Zhang
a   College of Arts and Sciences, Shanxi Agricultural University, Taigu 030801, P. R. of China
,
Yongqiang Wang∗
b   Department of Chemistry & Materials Science, Northwest University, Xi’an 710069, P. R. of China
,
Jinzhong Zhao∗
a   College of Arts and Sciences, Shanxi Agricultural University, Taigu 030801, P. R. of China
› Author AffiliationsWe 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).
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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.

Key words

alkenylation - palladium catalysis - C−H activation - carbazoles

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1387-5435.
  • Supporting Information

Primary Data



Publication History

Received: 17 December 2020

Accepted after revision: 09 February 2021

Accepted Manuscript online:
09 February 2021

Article published online:
30 March 2021

© 2021. Thieme. All rights reserved

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  • 30 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.