One-Pot Hydrosilylation-RCM-Protodesilylation:
Application to the Synthesis of ω-Alkenyl α,β-Unsaturated
Lactones

Cyril Bressy; Frédéric Bargiggia; Mathieu Guyonnet; Stellios Arseniyadis; Janine Cossy

doi:10.1055/s-0028-1087910

LETTER

One-Pot Hydrosilylation-RCM-Protodesilylation: Application to the Synthesis of ω-Alkenyl α,β-Unsaturated Lactones

Cyril Bressy, Frédéric Bargiggia, Mathieu Guyonnet, Stellios Arseniyadis, Janine Cossy*
Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS, 10 Rue Vauquelin, 75231 Paris Cedex 05, France
Fax: +33(1)40794660; e-Mail: janine.cossy@espci.fr;

Abstract

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Abstract

A simple and efficient one-pot procedure has been developed for the synthesis of α,β-unsaturated lactones bearing a pendant E-olefin. This new methodology, which features a hydrosilylation, a ring-closing metathesis (RCM) and a protodesilylation reaction, allows to perform RCM on substrates containing an alkyne moiety. The utility of this methodology was further demonstrated in the total synthesis of (+)-goniothalamin and (-)-pironetin, two natural products with interesting biological activities.

Key words

hydrosilylation - ring-closing metathesis - protodesilylation - α,β-unsaturated lactones - goniothalamin - pironetin

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References and Notes

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General Procedure for the One-Pot Hydrosilylation-RCM-Protodesilylation To a solution of alkyne (1 equiv) in CH₂Cl₂ (0.1 M solution) at 0 ˚C was added triethoxysilane (1.2 equiv) followed by Cp*Ru(MeCN)₃PF₆ (0.01 equiv). The flask was immediately allowed to warm to r.t. and stirred until complete conversion of the starting material. Grubbs’ second-generation catalyst was then added (0.05 equiv), and the reaction mixture was stirred at 40 ˚C until complete conversion. The reaction mixture was then allowed to reach r.t. before AgF (2.4 equiv) was added followed by MeOH (0.01 M), H₂O (0.01 M), and THF (0.1 M). Stirring was continued in the absence of light until complete consumption of the silylated intermediate, and the reaction mixture was filtered through Celite, extracted with CH₂Cl₂, dried over MgSO₄, and evaporated under reduced pressure. The crude residue was purified by flash column chromatography on SiO₂ using a gradient of eluents to afford the desired lactone.
Representative Characterization Data for Selected Products Compound 2a: IR: 2960, 2920, 2870, 1720, 1380, 1240, 980, 820 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 6.81 (dt, J = 9.6, 4.3 Hz, 1 H), 6.07 (dt, J = 9.6, 1.8 Hz, 1 H), 5.82 (dtd, J = 15.4, 5.8, 1.0 Hz, 1 H), 5.58 (ddt, J = 15.4, 6.6, 1.5 Hz,
1 H), 4.87 (q_app, J = 7.3 Hz, 1 H), 2.45-2.39 (m, 2 H), 2.04 (q_app, J = 6.8 Hz, 2 H), 1.41 (h_app, J = 7.3 Hz, 2 H), 0.90 (t, J = 7.3 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.2 (s), 144.7 (d), 135.5 (d), 126.9 (d), 121.6 (d), 78.3 (d), 34.2 (t), 29.8 (t), 21.9 (t), 13.6 (q). ESI-HRMS: m/z calcd for C₁₀H₁₄NaO₂ [M + Na]⁺: 189.0891; found: 189.0886.
Compound 2c: IR: 2920, 1720, 1640, 1390, 1250, 820 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 6.87 (ddd, J = 9.8, 5.0, 3.0 Hz, 1 H), 6.01 (dt, J = 9.8, 2.0 Hz, 1 H), 5.78 (ddt, J = 17.2, 10.1, 6.6 Hz, 1 H), 5.01 (dq_app, J = 17.2, 2.0 Hz, 1 H), 5.01 (dq_app, J = 10.1, 3.3 Hz, 1 H), 4.41 (m, 1 H), 2.35-2.29 (m, 2 H), 2.14-2.01 (m, 2 H), 1.86-1.71 (m, 1 H), 1.70-1.56 (m, 2 H), 1.56-1.42 (m, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 163.5 (s), 144.0 (d), 137.0 (d), 120.4 (d), 114.0 (t), 76.8 (d), 32.3 (t), 31.2 (t), 28.4 (t), 22.9 (t). ESI-HRMS: m/z calcd for C₁₀H₁₄NaO₂ [M + Na]⁺: 189.0891; found: 189.0886.

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