Catalytic Activity Studies of Aminocarbonyl Group Containing Hoveyda-Grubbs-Type Complexes for the Syntheses of Herbarumin I and Stagonolide A

Abstract

The catalytic activity of four aminocarbonyl group containing ‘boomerang’-type ring-closing metathesis catalysts have been studied for ten-membered lactone and compared well with the Grubbs I and II as well as the Hoveyda-Grubbs catalysts. The activity was found to be superior to the above three ring-closing metathesis catalysts and suggesting novel stereoselective total syntheses of herbarumin I and stagonolide A.

decanolides - stagonolides - herbarumin I - Wittig reaction - ring-closing metathesis

References and Notes

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Analytical and Spectral Data of 10
[α]_D ^²5 +7.6 (c 1.1, CHCl₃). IR (neat): 3455, 2924, 2852, 2097, 1461 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.43-7.19 (m, 5 H), 6.05 (m, 1 H), 5.34 (dd, J = 17.3, 1.5 Hz, 1 H), 5.18 (dd, J = 10.6, 1.5 Hz, 1 H), 4.60 (ABq, J = 13.6, 11.3 Hz, 2 H), 4.31 (t, J = 5.3 Hz, 1 H), 3.74 (m, 1 H), 3.25 (t, J = 6.04 Hz, 1 H), 2.90 (br s, 1 H), 2.59 (br s, 1 H), 1.69-1.24 (m, 4 H), 0.92 (t, J = 6.8 Hz, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 137.7, 137.9, 137.7, 128.4, 127.8, 128.1, 116.1, 84.2, 73.9, 73.7, 72.6, 35.3, 18.8, 14.0. HRMS: m/z calcd for C₁₅H₂₂O₃Na: 273.1466; found: 273.1472.

<A NAME="RG05410ST-15">15</A>

Analytical and Spectral Data of 11
[α]_D ^²5 +27.0 (c 0.7, CHCl₃). IR (neat): ν_max = 3398, 2963, 2925, 2855, 1723, 1711, 1639, 1461, 1129 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.38-7.23 (m, 5 H), 6.02-5.68 (m,
2 H), 5.29-5.12 (m, 2 H), 5.07-4.95 (m, 2 H), 4.66 (ABq, J = 17.2, 11.5 Hz, 2 H), 4.21-4.06 (m, 2 H), 3.50 (t, J = 4.7 Hz, 1 H), 2.33-2.24 (m, 2 H), 2.14-2.06 (dd, J = 7.4, 6.9 Hz, 2 H), 1.78-1.63 (m, 4 H), 1.40-1.22 (m, 2 H), 0.96-0.84 (m, 12 H), 0.07 (s, 3 H), 0.04 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 172.7, 138.5, 138.1, 137.6, 128.2, 127.8, 127.5, 116.5, 115.3, 83.9, 74.6, 74.0, 73.7, 34.9, 33.7, 33.1, 31.5, 25.8, 24.1, 18.7, 14.0, -4.2, -5.0. HRMS: m/z calcd for C₂₇H₄₄O₄NaSi: 483.2906; found: 483.2914.

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<A NAME="RG05410ST-17">17</A>

Analytical and Spectral Data of 12
[α]_D ^²5 +18.2 (c 1.0, CHCl₃). IR (film): ν_max = 4272, 3801, 3471, 2954, 1722, 1641, 1371, 1217, 1091 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 7.40-7.30 (m, 5 H), 5.68-5.57 (m, 1 H), 5.50 (dd, J = 15.7, 1.1 Hz, 1 H), 5.21 (dt, J = 9.5, 1.1 Hz, 1 H), 4.73-4.53 (m, 3 H), 3.37 (dd, J = 9.6, 1.9 Hz, 1 H), 2.34-2.27 (m, 2 H), 2.03-1.78 (m, 4 H), 1.49 (m, 1 H), 1.36-1.22 (m, 4 H), 0.89 (t, J = 7.4 Hz, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 175.5, 137.3, 133.1, 130.3, 128.5, 128.0, 124.6, 80.9, 72.3, 68.8, 68.8, 34.5, 33.6, 33.5, 24.5, 17.8, 13.9. HRMS: m/z calcd for C₁₉H₂₆O₄Na: 341.1728; found: 341.1722.

<A NAME="RG05410ST-18">18</A>

General Procedure for the Metathesis Reaction
To a stirred solution of diene (1.0 mmol) in freshly prepared dry CH₂Cl₂ (200 mL) at r.t. was added the metathesis catalyst (0.01 mmol) under argon. The progress of the reaction was monitored by TLC. After completion of the reaction, solvent was removed under reduced pressure. The crude product was purified by flash column chromatography (EtOAc-hexane = 1:6) to afford the E-isomer as the sole product.

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<A NAME="RG05410ST-20">20</A>

Analytical and Spectral Data of 2
[α]_D ^²5 +10.6 (c 1.0, EtOH); lit.:^7b [α]_D ^²0 +10.8 (c 0.51, EtOH). ^¹H NMR (300 MHz, CDCl₃): δ = 5.61 (d, J = 15.9 Hz, 1 H), 5.49 (m, 1 H), 4.95 (td, J = 9.4, 2.2 Hz, 1 H), 4.42 (br s, 1 H), 3.51 (d, J = 9.8 Hz, 1 H), 2.76 (br s, 1 H), 2.45-2.25 (m, 2 H), 2.06-1.81 (m, 4 H), 1.56 (m, 1 H), 1.43-1.18 (m, 3 H), 0.91 (t, J = 7.3 Hz, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 176.3, 130.7, 124.6, 73.6, 73.3, 70.1, 34.4, 33.6, 33.3, 24.6, 17.9, 13.8. IR (neat): ν_max = 3455, 3038, 2955, 2920, 2867, 1711, 1639, 1219 cm^-¹. HRMS: m/z calcd for C₁₂H₂₀O₄Na: 251.1259; found: 251.1264.

<A NAME="RG05410ST-21">21</A>

Analytical and Spectral Data of 1
Mp 71-72 ˚C; [α]_D ^²5 -59.2 (c 0.5, EtOH). ^¹H NMR (300 MHz, CDCl₃): δ = 6.42 (d, J = 16.0 Hz, 1 H), 6.32 (m, 1 H), 4.65 (dt, J = 9.5, 2.4 Hz, 1 H), 4.05 (dd, J = 9.5, 6.2 Hz, 1 H), 3.57 (d, J = 6.2 Hz, 1 H), 2.57-2.41 (m, 2 H), 2.20-1.90 (m, 6 H), 1.43-1.18 (m, 3 H), 0.93 (t, J = 7.2 Hz, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 199.5, 174.2, 143.1, 131.9, 76.5, 74.4, 34.2, 34.0, 33.5, 24.9, 18.0, 13.7. IR (neat): ν_max = 3468, 2925, 1740, 1700, 1638, 1219 cm^-¹. HRMS: m/z calcd for C₁₂H₁₉O₄: 227.1278; found: 227.1274.