Synthesis of Substituted Cyclooctenes through Cross-Coupling Reactions

Ryuichi Murata; Rakuto Yoshida; Daisuke Uraguchi; Keisuke Asano

doi:10.1055/a-2330-0819

Synlett, Table of Contents

Synlett 2025; 36(01): 69-74
DOI: 10.1055/a-2330-0819

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Synthesis of Substituted Cyclooctenes through Cross-Coupling Reactions

Ryuichi Murata

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo, Kyoto 615-8510, Japan

,

Rakuto Yoshida

^bInstitute for Catalysis, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan

,

Daisuke Uraguchi ∗

^bInstitute for Catalysis, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan

^cList Sustainable Digital Transformation Catalyst Collaboration Research Platform, Institute for Chemical Reaction Design and Discovery (ICReDD List-PF), Hokkaido University, Sapporo, Hokkaido 001-0021, Japan

,

Keisuke Asano ∗

^bInstitute for Catalysis, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan

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Abstract

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Abstract

Cross-coupling methods for the introduction of various substituents onto the olefin moiety of cyclooctenes were developed. A range of 1-substituted cis-cyclooctenes were synthesized. These protocols unlocked routes to previously inaccessible derivatives, permitting the syntheses of cis-cyclooctenes bearing various functional groups. Moreover, the method was applied to the synthesis of a 1,2-disubstituted trans-cyclooctene for the first time, which proved to be a significantly more active organocatalyst than the previously developed monosubstituted trans-cyclooctene.

Key words

cyclooctenes - olefins - cross-coupling - organocatalysts

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References

References and Notes
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17 All of 9 was converted to provide several products, although the byproducts were not identified. The stability of 10a was sufficient for its isolation.
18 Nickel-Catalyzed Cross-Coupling; General Procedure 1-Bromocyclooctene (6) or 1,2-dibromocyclooctene (9; 0.50 mmol), the appropriate solvent (0.12 M), and NiCl₂(dppe) (13 mg, 0.025 mmol) were added sequentially to a flame-dried 10-mL test tube with a rubber septum under an argon atmosphere. The mixture was cooled to the reaction temperature and stirred for 10 min, and then the organomagnesium reagent 11 (0.75 or 1.3 mmol) was added over 10 min. The mixture was gradually warmed and stirred for the appropriate time. The reaction was then quenched with sat. aq NH₄Cl (2.0 mL). The resulting mixture was stirred at ambient temperature for 10 min, and then EtOAc (5.0 mL) and H₂O (5.0 mL) were added. The aqueous layer was extracted with EtOAc (3 × 10 mL), and the combined organic layers were dried (Na₂SO₄) and concentrated in vacuo. Purification of the crude product by flash column chromatography (silica gel, hexane) afforded the corresponding product 2 or 10a. Further purification by preparative recycling chromatography was conducted if necessary. (E)-1-Benzylcyclooctene (2a) [CAS Reg. No. 1870003-16-9] Colorless oil; yield: 90 mg (90%); TLC: R_f = 0.75 (hexane). ¹H NMR (600 MHz, CDCl₃): δ = 7.29–7.26 (m, 3 H), 7.19 (m, 2 H), 5.38 (t, J = 8.1 Hz, 1 H), 3.30 (s, 2 H), 2.12–2.09 (m, 4 H), 1.49–1.39 (m, 8 H). ¹³C NMR (150 MHz, CDCl₃): δ = 140.4, 140.1, 129.2, 128.1, 125.84, 125.82, 44.0, 30.0, 28.5, 28.4, 26.5, 26.4, 26.3. (E)-1,2-Dibenzylcyclooctene (10a) Colorless oil; yield: 1.3 mg (5%); TLC: R_f = 0.75 (hexane). IR (neat): 2922, 1466, 750, 727, 694 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 7.27–7.25 (m, 4 H), 7.19–7.18 (m, 6 H), 3.58 (s, 4 H), 2.19 (m, 4 H), 1.44–1.36 (m, 8 H). ¹³C NMR (150 MHz, CDCl₃): δ = 140.9, 133.5, 128.9, 128.2, 125.8, 38.4, 30.6, 29.2, 26.6. HRMS (EI); m/z [M⁺] calcd for C₂₂H₂₆: 290.20290; found: 290.20318.

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