Iridium-Catalyzed Asymmetric Allylation of Indoles via Kinetic Resolution of 1-Alken-4-yn-3-ols

Takahiro Sawano; Yuki Yasumura; Kyohei Kuwabara; Hikaru Sugiura; Kana Takahashi; Eri Ishikawa; Ryo Takeuchi

doi:10.1055/a-2108-9720

Synlett, Table of Contents

Synlett 2023; 34(20): 2491-2495
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

Takahiro Sawano

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

,

Yuki Yasumura

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

,

Kyohei Kuwabara

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

,

Hikaru Sugiura

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

,

Kana Takahashi

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

,

Eri Ishikawa

^bDepartment of Applied Chemistry, Chubu University, 1200 Matsumoto-cho, Kasugai 487-8501, Japan

,

Ryo Takeuchi∗

^aDepartment of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan

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Abstract

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Dedicated to Prof. Hisashi Yamamoto on the occasion of his 80^th 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.

Key words

iridium - asymmetric catalysis - allylation - 1-alken-4-yn-3-ols - indoles

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References

References and Notes
1 New address: T. Sawano, Department of Materials for Energy, Shimane University, 1060 Nishikawatsu-cho, Matsue, Shimane 690-8504, Japan.

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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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