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Synlett 2024; 35(05): 586-592
DOI: 10.1055/a-2021-7944
DOI: 10.1055/a-2021-7944
cluster
Biomimetic Synthesis
Bioinspired Formal Synthesis of Pancracine via Selective Hydrogenation of an Indole Derivative
This work was supported by the National Natural Science Foundation of China (21971018 and 82225041). The authors gratefully thank the Beijing Municipal Government and Tsinghua University for their financial support.
Abstract
A bioinspired formal synthesis of the montanine-type Amaryllidaceae alkaloid pancracine through selective hydrogenation of a 3-arylindole derivative is disclosed. The key features of this synthesis include a hexahydroindole synthesis by a chemoselective hydrogenation of an aryl-substituted indole and a diastereoselective silyl hydride reduction of an iminium intermediate generated from an enaminone through Tf2O activation. The eight-step assembly of the 5,11-methanomorphanthridine framework represents a novel and efficient strategy that permits one of the shortest syntheses of pancracine reported so far.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2021-7944.
- Supporting Information
Publication History
Received: 07 January 2023
Accepted after revision: 28 January 2023
Accepted Manuscript online:
28 January 2023
Article published online:
28 February 2023
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- 62 Procedure for the Selective Hydrogenation of 11c A solution of compound 11c (100 mg, 0.29 mmol, 1.0 equiv) in 50:1 HFIP–TFA (2.5 mL) was stirred in the presence of 50 wt % Pd/C at 50 ℃ under H2 at atmospheric pressure for 24 h. The mixture was then cooled to r.t. and filtered through Celite. The filtrate was basified with sat. aq NaHCO3, and the mixture was extracted with CH2Cl2 (×3). The combined organic layer was washed with brine, dried (Na2SO4), and concentrated under reduced pressure to give a crude residue that was purified by column chromatography (silica gel, 0.5–5% MeOH–CH2Cl2) to give 14c as a light-red solid; yield: 36 mg (48%). 1H NMR (400 MHz, DMSO-d 6): δ = 7.30 (s, 1 H), 6.76 (d, J = 7.9 Hz, 1 H), 6.64 (d, J = 1.5 Hz, 1 H), 6.59 (dd, J = 8.0, 1.6 Hz, 1 H), 5.94 (s, 2 H), 4.06 (dd, J = 11.0, 4.5 Hz, 1 H), 3.87 (t, J = 10.9 Hz, 1 H), 3.22 (dd, J = 10.7, 4.7 Hz, 1 H), 2.43 (t, J = 5.8 Hz, 1 H), 2.38 (t, J = 6.6 Hz, 1 H), 2.11–2.03 (m, 2 H), 1.89 (p, J = 6.3 Hz, 2 H). 13C NMR (101 MHz, DMSO-d 6): δ = 188.86, 169.32, 147.10, 145.22, 139.92, 119.67, 110.98, 107.81, 107.30, 100.54, 54.99, 43.12, 36.31, 23.24, 22.20. Procedure for the Tf2O-Induced Diastereoselective Activation/Reduction Tf2O (28 mg, 0.1 mmol, 2.0 equiv) and EtMe2SiH (8.8mg, 0.1 mmol, 2.0 equiv) were added successively to a stirred solution of compound 21 (21 mg, 0.05 mmol, 1.0 equiv) in anhydrous CH2Cl2 (4 mL) at r.t. The mixture was stirred at r.t. for 24 h then quenched with sat. aq NaHCO3 and extracted with CH2Cl2 (×3). The combined organic layer was washed with brine, dried (Na2SO4), and concentrated under reduced pressure. The residue that was purified by column chromatography (silica gel, 1–5% EtOAc–PE) to give compound 22 (79 mg, 36% yield) and dia-22 (108 mg, 49% yield) in a combined 85% yield. 22 1H NMR (400 MHz, CDCl3): δ = 7.57 (d, J = 8.2 Hz, 2 H), 7.21 (d, J = 8.4 Hz, 2 H), 6.53 (d, J = 8.0 Hz, 1 H), 6.34 (dd, J = 8.0, 1.8 Hz, 1 H), 6.22 (d, J = 1.7 Hz, 1 H), 5.90 (d, J = 0.8 Hz, 2 H), 4.16–4.04 (m, 1 H), 3.90 (dd, J = 10.7, 7.5 Hz, 2 H), 3.35 (dd, J = 10.7, 4.0 Hz, 1 H), 2.65 (dq, J = 12.1, 3.9 Hz, 1 H), 2.41 (s, 3 H), 2.39–2.37 (m, 2 H), 2.09 (d, J = 14.1 Hz, 1 H), 1.79–1.63 (m, 1 H), 1.50 (dd, J = 25.6, 11.5 Hz, 1 H). 13C NMR (101 MHz, CDCl3): δ = 147.76, 146.53, 144.08, 143.92, 133.13, 132.99, 129.58, 127.47, 120.20, 118.0 (q, J C–F = 308.2 Hz), 108.24, 107.08, 101.02, 59.91, 56.39, 42.85, 29.11, 26.44, 21.46, 20.36. 19F NMR (376 MHz, CDCl3): δ = –74.74. dia-22 1H NMR (400 MHz, CDCl3) δ = 7.68 (d, J = 8.3 Hz, 2 H), 7.39 (d, J = 7.9 Hz, 2 H), 6.75 (d, J = 1.0 Hz, 1 H), 6.70 (dd, J = 2.3, 1.0 Hz, 2 H), 5.94 (dd, J = 3.4, 1.5 Hz, 2 H), 3.80 (d, J = 8.1 Hz, 1 H), 3.48 (dd, J = 9.8, 2.4 Hz, 1 H), 3.39–3.35 (m, 1 H), 3.17 (dd, J = 9.8, 8.3 Hz, 1 H), 2.75–2.70 (m, 1 H), 2.47 (s, 3 H), 2.33–2.30 (m, 2 H), 2.15–2.09 (m, 1 H), 1.71–1.65 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 147.84, 146.68, 144.46, 143.30, 135.17, 134.99, 130.82, 129.88, 128.18, 121.22, 118.0 (q, J C–F = 321.6 Hz), 107.98, 107.62, 100.99, 61.27, 57.25, 43.36, 28.09, 26.63, 21.57, 20.48. 19F NMR (376 MHz, CDCl3): δ = –74.68.