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Synlett 2023; 34(20): 2491-2495
DOI: 10.1055/a-2108-9720
DOI: 10.1055/a-2108-9720
cluster
Special Issue Dedicated to Prof. Hisashi Yamamoto
Iridium-Catalyzed Asymmetric Allylation of Indoles via Kinetic Resolution of 1-Alken-4-yn-3-ols
This work was supported by Aoyama Gakuin University Research Institute grant program for promotion of SDGs-related research and a grant from Aoyama Gakuin Research Institute.
Dedicated to Prof. Hisashi Yamamoto on the occasion of his 80th birthday
Abstract
We report the iridium-catalyzed asymmetric allylation of indoles via kinetic resolution of 1-alken-4-yn-3-ols to form chiral 1-alken-4-yn-3-ols and branched allylated products with high selectivity. 1-Alken-4,6-diyn-3-ol was also found to be suitable for this asymmetric allylation and gave the products in high yield and enantioselectivity. Other nucleophiles such as a malonic ester and a thiol, besides indoles, reacted to give allylated products and 1-alken-4-yn-3-ols with high enantioselectivities.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2108-9720.
- Supporting Information
Publication History
Received: 30 April 2023
Accepted after revision: 12 June 2023
Accepted Manuscript online:
12 June 2023
Article published online:
17 July 2023
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- 18 Reaction of 1-Alken-4-yn-3-ol 1a with Indole (2a) A mixture of [Ir(cod)Cl]2 (8.4 mg, 0.0126 mmol) and (R)-L (39.1 mg, 0.0770 mmol) in THF (2.0 mL) was stirred at room temperature for 15 min. To the mixture was added 2a (58.7 mg, 0.501 mmol), 1a (157.7 mg, 0.9968 mmol), and Mg(OTf)2 (16.1 mg, 0.0499 mmol), and it was stirred at 50 °C for 4 h. After removal of the solvent on a rotary evaporator, the residue was subjected to column chromatography (silica gel, hexane/EtOAc = 95:5) to give compounds 3aa (118.2 mg, 0.4593 mmol, 92% yield, 99% ee) and 1a (72.0 mg, 0.455 mmol, 46% yield, >99% ee). 3-(5-Phenylpent-1-en-4-yn-3-yl)-1H-indole (3aa) Obtained as a red oil. The ee was measured by HPLC (Chiralcel OJ-H column; 1.0 mL/min; hexane/2-propanol = 80:20; 230 nm): t 1 = 39.8 min (major), t 2 = 49.0 min (minor); [α] d 24 –49 (c 1.01, CHCl3) for 99% ee. 1H NMR (500 MHz, CDCl3): δ = 7.98 (br, 1 H), 7.76 (d, J = 8.0 Hz, 1 H), 7.49–7.42 (m, 2 H), 7.35 (d, J = 8.0 Hz, 1 H), 7.32–7.25 (m, 3 H), 7.23–7.17 (m, 2 H), 7.16–7.10 (m, 1 H), 6.13 (ddd, J = 16.6, 9.8, 6.0 Hz, 1 H), 5.57–5.50 (m, 1 H), 5.25–5.18 (m, 1 H), 4.86 (d, J = 5.7 Hz, 1 H). 13C{1H} NMR (126 MHz, CDCl3): δ = 137.2, 136.7, 131.7, 128.2, 127.8, 126.0, 123.6, 122.2, 121.9, 119.54, 119.46, 115.1, 115.0, 111.3, 89.0, 83.7, 33.5. HRMS (FAB): m/z [M]+ calcd for C19H15N: 257.1199; found: 257.1197. (S)-5-Phenylpent-1-en-4-yn-3-ol (1a) Obtained as a colorless oil. The ee was measured by HPLC (Chiralcel OJ-H column; 1.0 mL/min; hexane/2-propanol = 90:10; 230 nm): t 1 = 14.7 min (minor), t 2 = 17.7 min (major); [α] d 24 +46 (c 1.00, CHCl3) for >99% ee. 1H NMR (500 MHz, CDCl3): δ = 7.49–7.41 (m, 2 H), 7.36–7.27 (m, 3 H), 6.07 (ddd, J = 17.2, 10.0, 5.3 Hz, 1 H), 5.59–5.51 (m, 1 H), 5.31–5.25 (m, 1 H), 5.11 (t, J = 6.0 Hz, 1 H), 2.12–1.98 (m, 1 H). 13C{1H} NMR (126 MHz, CDCl3): δ = 136.9, 131.7, 128.6, 128.3, 122.3, 116.6, 87.6, 86.3, 63.7. HRMS (FAB): m/z [M]+ calcd for C11H10O: 158.0726; found: 158.0722.
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